Active energy curing type composition for in-place shaping gasket and in-place shaped gasket

ABSTRACT

An active energy curing type composition for an in-place shaping gasket is provided which is capable of providing an in-place shaped gasket superior in heat resistance, weather resistance, oil resistance, curability, compression set, and the like. An active energy curing type composition for an in-place shaping gasket, comprising the under-mentioned components (A) and (B) as essential components, wherein the viscosity of the composition is 400 Pa·s or less at 23° C. and the compression set of a cured article which is prescribed in JIS K 6262 is 30% or less: (A) a vinyl polymer having two or more (meth)acryloyl groups per molecule at the molecular ends, and (B) a vinyl polymer having one (meth)acryloyl group per molecule at the molecular end.

TECHNICAL FIELD

The present invention relates to an active energy curing typecomposition for an in-place shaping gasket and an in-place shaped gasketproduced using the composition. More specifically, the present inventionrelates to an active energy curing type composition for an in-placeshaping gasket comprising vinyl polymers having (meth)acryloyl groups atthe molecular ends as essential components and an in-place shaped gasketproduced using the composition.

BACKGROUND ART

An acrylic rubber is used as functional parts, security parts, and thelike centralized in the surrounding of the engine of automobiles and agasket is one of major product forms among them.

However, the gasket is obtained by kneading compounding agents such as afilling agent and a vulcanizing agent with an unvulcanized rubber andthen molding the mixture by vulcanization, but in case of the acrylicrubber, there are problems that since the rubber adheres on a roll onkneading, is hardly smoothed on sheeting, or is non flowable on molding,processability is poor and since vulcanization speed is slow orpost-cure for a long time is required, curability is poor. Further,there are also problems such as the reliability of sealing and thenecessity of high-precision processing of flange face.

Those in which processability and curability were improved are reported(Patent Document 1), but it does not enable the improvement ofproductivity by optical curing which enables rapid curing.

Further those in which a silicone material or an urethane (meth)acrylateresin is a main component are used as a gasket material, but when thesilicone material is used, damage is serious when SJ grade engine oilbeing recent high performance engine oil, transmission oil for anautomatic car and a portion of gear oil are used; therefore it has beenin a situation that such damage cannot be solved by conventionaltechnology such as a method of compounding basic zinc carbonate in whichthe contents of iminoxysilane and zinc hydroxide is 5 to 50% by weight(hereinafter, referred to as %) (Patent Document 2).

On the other hand, when those in which the urethane (meth)acrylate resinis a main component are used, there are those superior in oil resistance(Patent Document 3), but since it has ether bonds or ester bonds in mainchain, there is a problem in heat resistance for a long time.

The present inventors have hitherto reported a polymer in which its mainchain is an acrylic polymer obtained by living radical polymerizationand which has a (meth)acryloyl group at its ends (Patent Documents 4 and5), but compression set which is essential physical property as a gasketis not described.

-   Patent Document 1: JP-A-2000-154370-   Patent Document 2: JP-A-3-203960-   Patent Document 3: JP-A-64-112-   Patent Document 4: JP-A-2000-72816-   Patent Document 5: JP-A-2000-95826

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention

It is an object of the present invention to provide an active energycuring type composition for an in-place shaping gasket superior incurability capable of providing an in-place shaping gasket which issuperior in heat resistance, weather resistance, oil resistance,compression set, and the like, and an in-place shaped gasket producedusing the composition.

Means for Solving the Problem

The present invention relates to an active energy curing typecomposition for an in-place shaping gasket comprising the constitutionbelow and an in-place shaped gasket produced using the composition.

Namely, the present invention relates to an active energy curing typecomposition for an in-place shaping gasket, comprising theunder-mentioned components (A) and (B) as essential components, whereinthe viscosity of the composition is 400 Pa·s or less at 23° C. and thecompression set (obtained by a procedure wherein strain after compressedby 25% at 150° C. for 70 hours is measured and the strain which is notrestored after the release of compression is expressed in terms ofpercentage, provided that the quantity of compression applied is 100%)of a cured article which is prescribed in JIS K 6262 is 30% or less.

(A) a vinyl polymer having two or more groups represented by generalformula (1):—OC(O)C(R^(a))═CH₂  (1)wherein R^(a) represents a hydrogen atom or an organic group having 1 to20 carbon atoms, per molecule at the molecular ends.

(B) a vinyl polymer having one group represented by general formula (1)per molecule at the molecular end.

Herein, the above-mentioned component (A) means a vinyl polymer moleculehaving two or more groups represented by the above-mentioned generalformula (1). Further, when component (A) is produced, side reactionoccurs actually; therefore the average value of the number of groupsrepresented by general formula (1) in a mixture of vinyl polymersproduced is occasionally less than 2. However, in the present invention,when the average value of the number of groups represented by generalformula (1) in the mixture is 1.1 or more with respect to the mixture ofthe vinyl polymers practically produced, the mixture can be called ascomponent (A).

Herein, the above-mentioned component (B) means a vinyl polymer moleculehaving one group represented by general formula (1). Further, whencomponent (B) is produced, side reaction occurs actually; therefore theaverage value of the number of groups represented by general formula (1)in a mixture of vinyl polymers produced is occasionally less than 1.However, in the present invention, even if the average value of thenumber of groups represented by general formula (1) in the mixture is1.0 or less with respect to the mixture of the vinyl polymerspractically produced, the mixture can be called as component (B).

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein the vinyl monomerconstituting the main chain of component (A) or (B) comprises a(meth)acrylic monomer as a main component. In the present invention, therepresentation that the (meth)acrylic monomer is a main component meansthat the (meth)acrylic monomer is contained by at least 60% by weight inthe whole monomer.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein the vinyl monomerconstituting the main chain of component (A) or (B) comprises an acrylicacid ester monomer as a main component. In the present invention, therepresentation that the acrylic acid ester monomer is a main componentmeans that the acrylic acid ester monomer is contained by at least 60%by weight in the whole monomer.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein the vinyl monomerconstituting the main chain of component (A) or (B) contains at least 2monomers selected from butyl acrylate, ethyl acrylate and 2-methoxyethylacrylate.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein the viscosity of thevinyl polymer of component (B) is 100 Pa·s or less at 23° C.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein R^(a) is a hydrogenatom or a hydrocarbon group having 1 to 20 carbon atoms.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein R^(a) is a hydrogenatom or a methyl group.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, which is used for sealing asite at which oil resistance is required.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, which is used for sealing asite at which oil resistance and heat resistance are required.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, which is used in theperiphery of the engine of an automobile.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, which is used for sealingthe oil pan joint face of an automobile.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein the oil resistanceof the cured article of the composition for an in-place shaping gasketexceeds the oil resistance of the cured article of a compositioncomprising a polymer in which the repeating unit of vinyl polymer mainchains of components (A) and (B) is changed to butyl acrylate alone,with respect to at least one of items of the immersion test of JIS K6258 for lubricating oil Class 3 No. 5 for road vehicle prescribed inJIS K 2215.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein the oil resistanceof the cured article of the composition for an in-place shaping gasketis such that a mass change ratio after to before immersion is 50% orless, in the immersion test of JIS K 6258 for lubricating oil Class 3No. 5 for road vehicle prescribed in JIS K 2215.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein mass change ratioafter to before immersion is smaller than that of the cured article of acomposition comprising a polymer in which the repeating unit of vinylpolymer main chains of components (A) and (B) is changed to butylacrylate alone, in the immersion test of JIS K 6258 for lubricating oilClass 3 No. 5 for road vehicle prescribed in JIS K 2215.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein volume change ratioafter to before immersion is smaller than that of the cured article of acomposition comprising a polymer in which the repeating unit of vinylpolymer main chains of components (A) and (B) is changed to butylacrylate alone, in the immersion test of JIS K 6258 for lubricating oilClass 3 No. 5 for road vehicle prescribed in JIS K 2215.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein component (A) or (B)is produced by reacting a compound indicated by general formula (2):M⁺⁻OC(O)C(R^(a))═CH₂  (2)wherein R^(a) represents a hydrogen atom or an organic group having 1 to20 carbon atoms and M⁺ represents an alkali metal ion or a quaternaryammonium ion, with a vinyl polymer having halogen group(s) at theend(s).

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket wherein the vinyl polymerhaving halogen group(s) at the end(s) has a group indicated by generalformula (3):—CR¹R²X  (3)wherein R¹ and R² represent a group bonded to the ethylenicallyunsaturated group of a vinyl monomer, and X represents a chlorine atom,a bromine atom or an iodine atom.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein component (A) or (B)is produced by reacting a compound indicated by general formula (4):X¹C(O)C(R^(a))═CH₂  (4)wherein R^(a) represents a hydrogen atom or an organic group having 1 to20 carbon atoms, and X¹ represents a chlorine atom, a bromine atom or ahydroxyl group, with a vinyl polymer having hydroxyl group(s) at theend(s).

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein component (A) or (B)is produced by:

(1) reacting a diisocyanate compound with a vinyl polymer havinghydroxyl group(s) at the end(s), and

(2) reacting a compound indicated by general formula (5):HO—R′—OC(O)C(R^(a))═CH₂  (5)wherein R^(a) represents a hydrogen atom or an organic group having 1 to20 carbon atoms and R′ represents a divalent organic group having 2 to20 carbon atoms, with the residual isocyanate group.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein the main chain ofcomponent (A) or (B) is produced by a living radical polymerization of avinyl monomer.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein the living radicalpolymerization is atom transfer radical polymerization.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein a transition metalcomplex being the catalyst of the atom transfer radical polymerizationis selected from complexes of copper, nickel, ruthenium and iron.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein the transition metalcomplex is a complex of copper.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein the main chain ofcomponent (A) or (B) is produced by the polymerization of a vinylmonomer using a chain transfer agent.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein component (A) has anumber average molecular weight of 3,000 or more.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein the vinyl polymer ofcomponent (A) or (B) has a ratio of weight average molecular weight tonumber average molecular weight of less than 1.8 determined by gelpermeation chromatography.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, which further contains aphotopolymerization initiator (C) in addition to components (A) and (B).

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, which further contains amonomer and/or an oligomer having a radical polymerizable group.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, which further contains amonomer and/or an oligomer having an anionic polymerizable group.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, which contains a monomerand/or an oligomer having a (meth)acryloyl group.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, which contains a monomerand/or an oligomer having a (meth)acryloyl group and having a numberaverage molecular weight of 5,000 or less.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein thephotopolymerization initiator of component (C) is a radicalphotoinitiator.

A preferable embodiment of the present invention relates to thecomposition for an in-place shaping gasket, wherein thephotopolymerization initiator of component (C) is an anionicphotoinitiator.

A preferable embodiment of the present invention relates to an in-placeshaped gasket comprising the active energy curing type composition foran in-place shaping gasket.

A preferable embodiment of the present invention relates to an in-placeshaped gasket obtainable by irradiating the active energy curing typecomposition for an in-place shaping gasket with active energy radiation.

A preferable embodiment of the present invention relates to the in-placeshaped gasket, wherein the compression set (obtained by a procedurewherein strain after compressed by 25% at 150° C. for 70 hours ismeasured and the strain which is not restored after the release ofcompression is expressed in terms of percentage, provided that thequantity of compression applied is 100%) prescribed in JIS K 6262 is 20%or less.

A preferable embodiment of the present invention relates to the in-placeshaped gasket, wherein the compression set (obtained by a procedurewherein strain after compressed by 25% at 150° C. for 70 hours ismeasured and the strain which is not restored after the release ofcompression is expressed in terms of percentage, provided that thequantity of compression applied is 100%) prescribed in JIS K 6262 is 10%or less.

A preferable embodiment of the present invention relates to an activeenergy curing type composition for an in-place shaping gasket, which isobtainable by mixing the under-mentioned components (A) and (B), whereinthe viscosity of the composition is 400 Pa·s or less at 23° C. and thecompression set (obtained by a procedure wherein strain after compressedby 25% at 150° C. for 70 hours is measured and the strain which is notrestored after the release of compression is expressed in terms ofpercentage, provided that the quantity of compression applied is 100%)of a cured article which is prescribed in JIS K 6262 is 30% less.

(A) a mixture containing vinyl polymers having two or more groupsrepresented by general formula (1):—OC(O)C(R^(a))═CH₂  (1)wherein R^(a) represents a hydrogen atom or an organic group having 1 to20 carbon atoms, per molecule at the molecular ends, in which the numberof groups represented by general formula (1) in the vinyl polymers is1.1 or more on the average.

(B) a mixture containing vinyl polymers having one group represented bygeneral formula (1) per molecule at the molecular end, in which thenumber of groups represented by general formula (1) in the vinylpolymers is 1.0 or less on the average.

Effect of the Invention

An in-place shaped gasket which is superior in curability, heatresistance, weather resistance, oil resistance, compression set, and thelike can be provided by using an active energy curing type compositionfor an in-place shaping gasket in accordance with the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

The active energy curing type composition for an in-place shaping gasketin accordance with the present invention is described below.

<Component (A)>

Component (A) is a vinyl polymer having two or more groups per moleculeat the molecular ends, each group being represented by general formula(1) (hereinafter referred to as “(meth)acryloyl group” occasionally):—OC(O)C(R^(a))═CH₂  (1)wherein R^(a) represents a hydrogen atom or an organic group having 1 to20 carbon atoms.

It is necessary that the number of the (meth)acryloyl group in component(A) be more than one per molecule from the viewpoint of the curabilityof the curable composition (from the viewpoint of crosslinking). Anaverage introduction number is two or more per molecule. Herein, theaverage introduction number is a value obtained by dividing the totalnumber of the introduced ends by the number of molecules.

The (meth)acryloyl group exists at the molecular ends of the vinylpolymer from the viewpoint that rubber elasticity is obtained byuniformly enlarging molecular weight between crosslinking points, topreferably 500 to 100,000.

The R^(a) in the (meth)acryloyl group represents a hydrogen atom or anorganic group having 1 to 20 carbon atoms and is preferably a hydrogenatom or a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include analkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a nitrilegroup, and the like, and these may have a substitutent such as ahydroxyl group.

Examples of the alkyl group having 1 to 20 carbon atoms include a methylgroup, an ethyl group, a propyl group, a butyl group, a pentyl group, ahexyl group, an octyl group, a decyl group, and the like; examples ofthe aryl group having 6 to 20 carbon atoms include a phenyl group, anaphthyl group, and the like; and examples of the aralkyl group having 7to 20 carbon atoms include a benzyl group, a phenylethyl group, and thelike.

Specific examples of R^(a) in general formula (1) include, for example,—H, —CH₃, —CH₂CH₃, —(CH₂)_(n)CH₃ (n represents an integer of 2 to 19),—C₆H₅, —CH₂OH, —CN, and the like, and are preferably —H and —CH₃.

The vinyl monomer composing the main chain of component (A) is notspecifically limited and various monomers can be used. Examples thereofinclude (meth)acrylic monomers such as (meth)acrylic acid,methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate,isopropyl(meth)acrylate, n-butyl (meth)acrylate, isobutyl(meth)acrylate,tert-butyl(meth)acrylate, n-pentyl(meth)acrylate, n-hexyl(meth)acrylate,cyclohexyl (meth)acrylate, n-heptyl(meth)acrylate,n-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate,decyl(meth)acrylate, dodecyl(meth)acrylate, phenyl(meth)acrylate,tolyl(meth)acrylate, benzyl(meth)acrylate, 2-methoxyethyl(meth)acrylate,3-methoxybutyl (meth)acrylate, 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl (meth)acrylate, stearyl(meth)acrylate,glycidyl(meth)acrylate, 2-aminoethyl(meth)acrylate,γ-(methacryloyloxy)propyltrimethoxysilane, an ethylene oxide adduct of(meth)acrylic acid, trifluoromethylmethyl (meth)acrylate,2-trifluoromethylethyl(meth)acrylate,2-perfluoroethylethyl(meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl(meth)acrylate, 2-perfluoroethyl(meth)acrylate, perfluoromethyl(meth)acrylate,di-perfluoromethylmethyl(meth)acrylate,2-perfluoromethyl-2-perfluoroethylethyl(meth)acrylate,2-perfluorohexylethyl(meth)acrylate, 2-perfluorodecylethyl(meth)acrylate and 2-perfluorohexadecylethyl(meth)acrylate; aromaticvinyl monomers such as styrene, vinyl toluene, α-methylstyrene,chlorostyrene, and styrenesulfonic acid and its salt;fluorine-containing vinyl monomers such as perfluoroethylene,perfluoropropylene and vinylidene fluoride; silicon-containing vinylmonomers such as vinyl trimethoxysilane and vinyl triethoxysilane;maleic anhydride, maleic acid, mono alkyl esters and dialkyl esters ofmaleic acid; fumaric acid, mono alkyl esters and dialkyl esters offumaric acid; maleimide monomers such as maleimide, methylmaleimide,ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide,octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide andcyclohexylmaleimide; vinyl monomers containing a nitrile group such asacrylonitrile and methacrylonitrile; vinyl monomers containing an amidegroup such as acrylamide and methacrylamide; vinyl esters such as vinylacetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinylcinnamate; alkenes such as ethylene and propylene; conjugated dienessuch as butadiene and isoprene; vinyl chloride, vinylidene chloride,allyl chloride, allyl alcohol and the like. These may be used alone anda plurality of them may be also used in combination.

Among these, aromatic vinyl monomers and (meth)acrylic monomers arepreferable from the viewpoint of the physical properties of theresulting product. Acrylic acid ester monomers and methacrylic acidester monomers are more preferable and butyl acrylate, ethyl acrylateand 2-methoxyethyl acrylate are further preferable. The vinyl monomercomposing the main chain particularly preferably contains at least 2monomers selected from butyl acrylate, ethyl acrylate and 2-methoxyethylacrylate from the viewpoint of oil resistance and the like for anin-place shaping gasket.

In the present invention, these preferable monomers may be copolymerizedwith the fore-mentioned other monomers and in such case, thesepreferable monomers are preferably contained by at least 40% by weightratio.

The molecular weight distribution (the ratio of weight average molecularweight (Mw) to number average molecular weight (Mn) measured by gelpermeation chromatography (GPC)) of component (A) is not specificallylimited, but preferably less than 1.8, more preferably not more than1.7, further preferably not more than 1.6, particularly preferably notmore than 1.5, specifically preferably not more than 1.4 and the mostpreferably not more than 1.3.

For the measurement of molecular weight by GPC in the present invention,a polystyrene gel column is used usually using chloroform ortetrahydrofuran as mobile phase and the value of molecular weight isdetermined as a value converted to polystyrene.

The lower limit of the number average molecular weight of component (A)is preferably 500 and more preferably 3,000, and the upper limit ispreferably 100,000 and more preferably 40,000. When the molecular weightis less than 500, the natural property of the vinyl polymer tends to behardly expressed and when it exceeds 100,000, handling tends to bedifficult.

<Component (B)>

Component (B) is a vinyl polymer having one group represented by generalformula (1) ((meth)acryloyl group) per molecule at the molecular end andit is preferable from the viewpoint of rubber elasticity after curingthat it has one (meth)acryloyl group and the group exists at themolecular end.

The vinyl monomer composing the main chain of component (B) is notspecifically limited and various monomers can be used. As the specificexamples, the same monomers as the vinyl monomers composing the mainchain of component (A) can be used, and its use manner, preferred vinylmonomers and the like are also the same as those for the vinyl monomerscomposing the main chain of component (A).

The molecular weight distribution (the ratio of weight average molecularweight (Mw) to number average molecular weight (Mn) measured by gelpermeation chromatography (GPC)) of component (B) is not specificallylimited, but preferably less than 1.8, more preferably not more than1.7, further preferably not more than 1.6, particularly preferably notmore than 1.5, specifically preferably not more than 1.4 and the mostpreferably not more than 1.3.

The lower limit of the number average molecular weight of component (B)is preferably 500 and more preferably 2,000, and the upper limit ispreferably 100,000 and more preferably 40,000. When the molecular weightis less than 500, the natural property of the vinyl polymer tends to behardly expressed and when it exceeds 100,000, handling tends to bedifficult.

Since a purpose of the use of component (B) is to reduce the viscosityof the composition, the viscosity at 23° C. of component (B) ispreferably not more than 100 Pa·s.

The amount of component (B) used is not specifically limited, but ispreferably 5 to 200 parts (parts by weight, hereinafter the same) basedon 100 parts of component (A) and more preferably 10 to 100 parts. Whenit is less than 5 parts, the effect of reducing the viscosity of thecomposition is poor and when it exceeds 200 parts, tendency to lower thecurability is generated.

<Manufacturing Process of Components (A) and (B)>

The manufacturing process of components (A) and (B) is not specificallylimited.

The vinyl polymer is generally produced by anion polymerization orradical polymerization, but the radical polymerization is preferablefrom the viewpoint of the versatility of the monomer or the easiness ofcontrol. Among the radical polymerizations, living radicalpolymerization and radical polymerization using a chain transfer agentare more preferable and the former is preferable in particular.

The radical polymerization process used for the production of components(A) and (B) can be classified as “general radical polymerizationprocess” in which a monomer having a specific functional group and avinyl monomer are merely copolymerized using an azo compound, a peroxideor the like as a polymerization initiator and “controlled radicalpolymerization process” in which a specific functional group can beintroduced into a controlled position such as the end of a polymer.

The “general radical polymerization process” is a simple process butsince a monomer having a specific functional group is onlyprobabilistically introduced into the polymer, a large quantity of themonomer is required when a polymer having high functionalized rate isdesigned to be obtained. To the contrary, there is a problem that smallamount of the monomer used increases the proportion of a polymer inwhich a specific functional group is not introduced. Further, since itis free radical polymerization, there is a problem that only a polymerhaving a wide molecular weight distribution and a high viscosity isobtained.

Further, the “controlled radical polymerization” can be classified as“chain transfer agent process” in which a vinyl polymer havingfunctional groups at the ends is obtained by carrying out polymerizationusing a chain transfer agent having a specific functional group, and“living radical polymerization process” in which polymerizationpropagation terminal is grown without provoking termination reaction andthereby a polymer with nearly designed molecular weight is obtained.

The “chain transfer agent process” can provide a polymer having highfunctionalized rate but a remarkably large quantity of chain transferagent having a specific functional group is necessary against aninitiator, resulting in an economical problem including treatment.Further, like the above-mentioned “general radical polymerizationprocess”, since it is free radical polymerization, there is a problemthat only a polymer having a wide molecular weight distribution and ahigh viscosity is obtained.

Differing from these polymerization processes, the “living radicalpolymerization process” is characterized as follows: it is high inpolymerization speed; termination reaction occurs hardly nevertheless itis radical polymerization in which termination reactions due to couplingof radicals easily occur and control is difficult; a polymer with narrowmolecular weight distribution (Mw/Mn is about 1.1 to 1.5) is obtained;and the molecular weight can be freely controlled according to thecharge ratio of a monomer to an initiator.

Accordingly, the “living radical polymerization process” can provide apolymer with narrow molecular weight distribution and low viscosity andadditionally, since a monomer having a specific functional group can beintroduced at nearly arbitrary position, it is more preferable as themanufacturing process of the vinyl polymer having the specificfunctional group.

The living polymerization means polymerization in which terminal keepsalways activity and molecular chains continue to grow in the narrowsense, but in general, it includes also quasi living polymerization inwhich those in which the terminal is deactivated and those in which theterminal is activated are in an equilibrium state to keep growth. Thedefinition in the present invention is also the latter.

The “living radical polymerization process” has been recently studied byvarious groups.

Examples thereof include a process using a cobalt porphyrin complexshown in J. Am. Chem. Soc. 1994, Vol. 116, pp 7943, a process using aradical scavenger such as a nitroxide compound shown in Macromolecules1994, Vol. 27, pp 7228, “Atom Transfer Radical Polymerization (ATRP)” inwhich an organic halide is used as an initiator and a transition metalcomplex is a catalyst, and the like.

Among the “living radical polymerization processes”, the “atom transferradical polymerization process” in which a vinyl monomer is polymerizedusing an organic halide or a halogenated sulfonyl compound or the likeas an initiator and a transition metal complex as a catalyst hasadvantages that the resulting polymer has at the ends halogen and thelike which are comparatively advantageous for functional groupconversion reaction and that the freedom of design of the initiator andcatalyst is great in addition to the characteristic of theafore-mentioned “living radical polymerization process”; therefore it isfurther preferable as the manufacturing process of the vinyl polymerhaving a specific functional group.

Examples of the “atom transfer radical polymerization process” includeprocesses described in Matyjaszewski et al, J. Am. Chem. Soc., 1995,Vol. 117, pp 5614, Macromolecules 1995, Vol. 28, pp 7901, Science 1996,Vol. 272, pp 866, WO96/30421 pamphlet, WO97/18247 pamphlet, and Sawamotoet. al., Macromolecules, 1995, Vol. 28, pp 1721.

In the present invention, there is no limitation as to which processamong these processes is used, but basically, the controlled radicalpolymerization process is utilized, and the living radicalpolymerization process is preferable because of easy control and inparticular, the atom transfer radical polymerization process is morepreferable.

Firstly, polymerization process using a chain transfer agent among thecontrolled radical polymerization processes is described.

Radical polymerization using a chain transfer agent (telomer) is notspecifically limited, but the following two methods are exemplified as aprocess of obtaining the vinyl polymer having a terminal structuresuitable for the present invention.

They are a process for obtaining a polymer having halogen terminal usinghalogenated hydrocarbon as a chain transfer agent shown in JP-A-4-132706and a process for obtaining a polymer having hydroxyl group terminalusing hydroxyl group-containing mercaptan or hydroxyl group-containingpolysulfide or the like as a chain transfer agent shown inJP-A-61-271306, JP-B-2594402 and JP-A-54-47782.

Then, the living radical polymerization process is described.

Among them, firstly, a process of using a radical scavenger (radicalcapping agent) such as a nitroxide compound is described.

In the polymerization process, stable nitroxy free radical (═N—O.) isgenerally used as a radical capping agent. The compound is notspecifically limited, but nitroxy free radicals from cyclichydroxylamines, such as 2,2,6,6-substituted-1-piperidinyloxy radical and2,2,5,5-substituted-1-pyrrolidinyloxy radical, are preferable. As thesubstitutent, alkyl groups having at most 4 carbon atoms such as amethyl group and an ethyl group are suitable.

Specific examples of the nitroxy free radical compound are notspecifically limited, but include 2,2,6,6-tetramethyl-1-piperidinyloxyradical (TEMPO), 2,2,6,6-tetraethyl-1-piperidinyloxy radical,2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical,2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical,1,1,3,3-tetramethyl-2-isoindolinyloxy radical, N,N-di-t-butylaminoxyradical.

Stable free radical such as galvinoxyl free radical may be used in placeof the afore-mentioned nitroxy free radicals.

The radical capping agent is used in combination with a radicalgenerating agent. It is considered that the reaction product of theradical capping agent with radical generating agent becomes apolymerization initiator and thereby, the polymerization of an additionpolymerizable monomer proceeds.

The proportion of both agents used is not specifically limited, but theradical generating agent is suitably 0.1 to 10 moles based on 1 mole ofthe radical capping agent.

As the radical generating agent, various compounds can be used, butperoxides capable of generating radical under the condition ofpolymerization temperature are preferable.

The peroxides are not specifically limited, but examples thereof includediacyl peroxides such as benzoyl peroxide and lauroyl peroxide; dialkylperoxides such as dicumyl peroxide and di-tert-butyl peroxide; peroxycarbonates such as diisopropylperoxy dicarbonate andbis(4-t-butylcyclohexyl)peroxy dicarbonate; alkyl peresters such ast-butylperoxy octanoate and t-butylperoxy benzoate. In particular,benzoyl peroxide is preferable.

Further, radical generating azo compounds such as azobisisobutyronitrilecan be used in place of peroxide.

As reported in Macromolecules, 1995, Vol. 28, pp 2993, an alkoxyaminecompound described below may be used in place of using the radicalcapping agent and the radical generating agent in combination.

In the case that the alkoxyamine compound is used as an initiator, apolymer having a functional group at the end is obtained when a compoundhaving a functional group such as hydroxyl group like theabove-mentioned is used. When this is utilized in the present invention,a polymer having a functional group at the end can be obtained.

A monomer, a solvent, and polymerization conditions such aspolymerization temperature which are used in polymerization using theradical capping agent such as the nitroxide compound are notspecifically limited, but may be similar to those used in the atomtransfer radical polymerization which is described below.

Then, the atom transfer radical polymerization process which is morepreferable as the living radical polymerization process used in thepresent invention is described.

In the atom transfer radical polymerization, an organic halide, inparticular, an organic halide having a high reactive carbon-halogen bond(for example, a carbonyl compound having halogen at α-position, acompound having halogen at a benzyl position), a halogenated sulfonylcompound, or the like is used as an initiator.

Specific examples thereof include:

-   C₆H₅—CH₂X, C₆H₅—C(H)(X)CH₃, C₆H₅—C(X)(CH₃)₂,    wherein C₆H₅ represents a phenyl group and X represents a chlorine    atom, a bromine atom or an iodine atom;-   R³—C(H)(X)—CO₂R⁴, R³—C(CH₃)(X)—CO₂R⁴, R³—C(H)(X)—C(O)R⁴,-   R³—C(CH₃)(X)—C(O)R⁴,    wherein R³ and R⁴ are a hydrogen atom, an alkyl group having 1 to 20    carbon atoms, an aryl group having 6 to 20 carbon atoms or an    aralkyl group having 7 to 20 carbon atoms, and X is a chlorine atom,    a bromine atom or an iodine atom; and-   R³—C₆H₄—SO₂X,    wherein R³ is a hydrogen atom, an alkyl group having 1 to 20 carbon    atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group    having 7 to 20 carbon atoms, and X is a chlorine atom, a bromine    atom or an iodine atom.

As the initiator of the atom transfer radical polymerization process, anorganic halide or a halogenated sulfonyl compound having a functionalgroup other than a functional group initiating polymerization can bealso used. In such a case, a vinyl polymer having the functional groupat one end of a main chain and the structure represented by generalformula (1) at the other end of the main chain is produced.

Examples of the functional group include an alkenyl group, acrosslinking silyl group, a hydroxyl group, an epoxy group, an aminogroup, and an amide group.

The organic halide having an alkenyl group is not specifically limited,and there are exemplified those indicated by general formula (6):R⁶R⁷C(X)—R⁸—R⁹—C(R⁵)═CH₂  (6)wherein R⁵ is a hydrogen atom or a methyl group, R⁶ and R⁷ are ahydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl grouphaving 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbonatoms or those which are mutually linked at another end, R⁸ is —C(O)O—(an ester group), —C(O)— (a keto group) or an o-, m-, p-phenylene group,R⁹ is a direct bond or a divalent organic group having 1 to 20 carbonatoms which may optionally contain at least one ether bond, and X is achlorine atom, a bromine atom or an iodine atom.

Specific examples of the substitutents R⁶ and R⁷ include a hydrogenatom, a methyl group, an ethyl group, a n-propyl group, an isopropylgroup, a butyl group, a pentyl group, and a hexyl group. R⁶ and R⁷ mayoptionally be bonded at another end to form a ring skeleton.

Examples of the divalent organic group having 1 to 20 carbon atomsindicated by R⁹ and which may optionally contain at least one ether bondinclude an alkylene group having 1 to 20 carbon atoms which mayoptionally contain at least one ether bond, and the like.

Specific examples of the organic halide having an alkenyl groupindicated by general formula (6) include:

wherein X is a chlorine atom, a bromine atom or an iodine atom, and n isan integer of 0 to 20;

wherein X is a chlorine atom, a bromine atom or an iodine atom, n is aninteger of 1 to 20 and m is an integer of 0 to 20;

-   o, m, p-XCH₂—C₆H₄—(CH₂)_(n)—CH═CH₂,-   o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂    wherein X is a chlorine atom, a bromine atom or an iodine atom, and    n is an integer of 0 to 20);-   o, m, p-XCH₂—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,-   o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)CH═CH₂    wherein X is a chlorine atom, a bromine atom or an iodine atom, n is    an integer of 1 to 20 and m is an integer of 0 to 20;-   o, m, p-XCH₂—C₆H₄—O—(CH₂)_(n)—CH═CH₂,-   o, m, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)_(n)—CH═CH₂,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)_(n)—CH═CH₂    wherein X is a chlorine atom, a bromine atom or an iodine atom, and    n is an integer of 0 to 20); and-   o, m, p-XCH₂—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,-   o, m, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂    wherein X is a chlorine atom, a bromine atom or an iodine atom, n is    an integer of 1 to 20 and m is an integer of 0 to 20.

The organic halides having an alkenyl group include further a compoundindicated by general formula (7):H₂C═C(R⁵)—R⁹—C(R⁶)(X)—R¹⁰—R⁷  (7)wherein R⁵, R⁶, R⁷, R⁹ and X are the same as the above-mentioned, andR¹⁰ represents a direct bond, —C(O)O— (an ester group), —C(O)— (a ketogroup) or an o-, m-, p-phenylene group.

R⁹ is a direct bond or a divalent organic group having 1 to 20 carbonatoms (at least one ether bond may be optionally contained), but in caseof the direct bond, a vinyl group is bonded to the carbon atom to whicha halogen atom is bonded, representing an allyl halide. In this case,since the carbon-halogen bond is activated by the adjacent vinyl group,the compound does not always contain a C(O)O group, a phenylene group orthe like as R¹⁰, and R¹⁰ may be a direct bond. When R⁹ is not a directbond, R¹⁰ is preferably a C(O)O group, a C(O) group or a phenylene groupto activate the carbon-halogen bond.

Specific examples of the compound indicated by general formula (7)include:

-   CH₂═CHCH₂X, CH₂═C(CH₃)CH₂X,-   CH₂═CHC(H)(X)CH₃, CH₂═C(CH₃)C(H)(X)CH₃,-   CH₂═CHC(X)(CH₃)₂, CH₂═CHC(H)(X)C₂H₅,-   CH₂═CHC(H)(X)CH(CH₃)₂,-   CH₂═CHC(H)(X)C₆H₅, CH₂═CHC(H)(X)CH₂C₆H₅,-   CH₂═CHCH₂C(H)(X)—CO₂R,-   CH₂═CH(CH₂)₂C(H)(X)—CO₂R,-   CH₂═CH(CH₂)₃C(H)(X)—CO₂R,-   CH₂═CH(CH₂)₈C(H)(X)—CO₂R,-   CH₂═CHCH₂C(H)(X)—C₆H₅,-   CH₂═CH(CH₂)₂C(H)(X)—C₆H₅,-   CH₂═CH(CH₂)₃C(H)(X)—C₆H₅    wherein X is a chlorine atom, a bromine atom or an iodine atom, and    R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an    aralkyl group.

Specific examples of the halogenated sulfonyl compound having an alkenylgroup include:

-   o-, m-, p-CH₂═CH—(CH₂)_(n)—C₆H₄—SO₂X,-   o-, m-, p-CH₂═CH—(CH₂)_(n)—O—C₆H₄—SO₂X    wherein X is a chlorine atom, a bromine atom or an iodine atom, and    n is an integer of 0 to 20.

The organic halide having a crosslinking silyl group is not specificallylimited and there are exemplified compounds indicated by general formula(8):R⁶R⁷C(X)—R⁸—R⁹—C(H)(R⁵)CH₂—[Si(R¹¹)_(2-b)(Y)_(b)O]_(m)—Si(R¹²)_(3-a)(Y)_(a)  (8)wherein R⁵, R⁶, R⁷, R⁸, R⁹ and X are the same as the above-mentioned;each of R¹¹ and R¹² indicates an alkyl group having 1 to 20 carbonatoms, an aryl group, an aralkyl group or a triorganosiloxy groupindicated by (R′)₃SiO— (R′ is a monovalent hydrocarbon group having 1 to20 carbon atoms and three R's may be the same or different) and when atleast two R¹¹s or R¹²s exist, they may be the same or different; Yindicates a hydroxyl group or a hydrolyzable group and when at least twoYs exist, they may be the same or different; a is 0, 1, 2 or 3, b is 0,1 or 2, m is an integer of 0 to 19, provided that a+mb≧1 is satisfied.

Specific examples of the compound indicated by general formula (8)include:

-   XCH₂C(O)O(CH₂)_(n)Si(OCH₃)₃,-   CH₃C(H)(X)C(O)O(CH₂)_(n)Si(OCH₃)₃,-   (CH₃)₂C(X)C(O)O(CH₂)_(n)Si(OCH₃)₃,-   XCH₂C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,-   CH₃C(H)(X)C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,-   (CH₃)₂C(X)C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂    wherein X is a chlorine atom, a bromine atom or an iodine atom, and    n is an integer of 0 to 20;-   XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,-   H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,-   (H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,-   CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,-   XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,-   H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)—Si(CH₃)(OCH₃)₂,-   (H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)—Si(CH₃)(OCH₃)₂,-   CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)—Si(CH₃)(OCH₃)₂    wherein X is a chlorine atom, a bromine atom or an iodine atom, n is    an integer of 1 to 20 and m is an integer of 0 to 20;-   o, m, p-XCH₂—C₆H₄—(CH₂)₂Si(OCH₃)₃,-   o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)₂Si(OCH₃)₃,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₂Si(OCH₃)₃,-   o, m, p-XCH₂—C₆H₄—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₃Si(OCH₃)₃,-   o, m, p-XCH₂—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,-   o, m, p-XCH₂—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)₃—Si(OCH₃)₃,-   o, m, p-XCH₂—C₆H₄—O—(CH₂)₂—O—(CH₂)₃—Si(OCH₃)₃,-   o, m, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,    wherein X is a chlorine atom, a bromine atom or an iodine atom.

The organic halides having a crosslinking silyl group include furthercompounds indicated by general formula (9).(R¹²)_(3-a)(Y)_(a)Si—[OSi(R¹¹)_(2-b)(Y)_(b)]_(m)—CH₂—C(H)(R⁵)—R⁹—C(R⁶)(X)—R¹⁰—R⁷  (9)wherein R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹¹, R¹², a, b, X and Y are the same as theabove-mentioned, and m is an integer of 0 to 19.

Specific examples of the compound indicated by general formula (9)include:

-   (CH₃O)₃SiCH₂CH₂C(H)(X)C₆H₅,-   (CH₃O)₂(CH₃)SiCH₂CH₂C(H)(X)C₆H₅,-   (CH₃O)₃Si(CH₂)₂C(H)(X)—CO₂R,-   (CH₃O)₂(CH₃)Si(CH₂)₂C(H)(X)—CO₂R,-   (CH₃O)₃Si(CH₂)₃C(H)(X)—CO₂R,-   (CH₃O)₂(CH₃)Si(CH₂)₃C(H)(X)—CO₂R,-   (CH₃O)₃Si(CH₂)₄C(H)(X)—CO₂R,-   (CH₃O)₂(CH₃)Si(CH₂)₄C(H)(X)—CO₂R,-   (CH₃O)₃Si(CH₂)₉C(H)(X)—CO₂R,-   (CH₃O)₂(CH₃)Si(CH₂)₉C(H)(X)—CO₂R,-   (CH₃O)₃Si(CH₂)₃C(H)(X)—C₆H₅,-   (CH₃O)₂(CH₃)Si(CH₂)₃C(H)(X)—C₆H₅,-   (CH₃O)₃Si(CH₂)₄C(H)(X)—C₆H₅,-   (CH₃O)₂(CH₃) Si(CH₂)₄C(H)(X)—C₆H₅    wherein X is a chlorine atom, a bromine atom or an iodine atom, and    R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an    aralkyl group.

The above-mentioned organic halide or halogenated sulfonyl compoundhaving a hydroxyl group is not specifically limited and those describedbelow are exemplified.

-   HO—(CH₂)_(n)—OC(O)C(H)(R)(X)    wherein X is a chlorine atom, a bromine atom or an iodine atom, R is    a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl    group or an aralkyl group, and n is an integer of 1 to 20.

The above-mentioned organic halide or halogenated sulfonyl compoundhaving an amino group is not specifically limited and those describedbelow are exemplified.

-   H₂N—(CH₂)_(n)—OC(O)C(H)(R)(X)    wherein X is a chlorine atom, a bromine atom or an iodine atom, R is    a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl    group or an aralkyl group, and n is an integer of 1 to 20.

The above-mentioned organic halide or halogenated sulfonyl compoundhaving an epoxy group is not specifically limited and those describedbelow are exemplified.

wherein X is a chlorine atom, a bromine atom or an iodine atom, R is ahydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl groupor an aralkyl group, and n is an integer of 1 to 20.

The organic halide or halogenated sulfonyl compound having two or moreinitiation points is preferably used as an initiator in order to obtaina vinyl polymer having two or more groups represented by general formula(1) per molecule at the molecular ends. Specific examples thereofinclude:

wherein C₆H₄ is a phenylene group, and X is a chlorine atom, a bromineatom or an iodine atom;

wherein R is an alkyl group having 1 to 20 carbon atoms, an aryl groupor an aralkyl group, and n is an integer of 0 to 20, and X is a chlorineatom, a bromine atom or an iodine atom;

wherein X is a chlorine atom, a bromine atom or an iodine atom, and n isan integer of 0 to 20;

wherein n is an integer of 1 to 20, and X is a chlorine atom, a bromineatom or an iodine atom;

wherein X is a chlorine atom, a bromine atom or an iodine atom.

The vinyl monomer used for the polymerization is not specificallylimited and all of them exemplified already can be preferably used.

The transition metal complex used as the polymerization catalyst is notspecifically limited, but is preferably a metal complex in which anelement of Groups 7, 8, 9, 10 or 11 of Periodic Table is a centralmetal, for example, complexes of copper, nickel, ruthenium and iron. Asthe more preferable complex, zerovalent copper complexes, monovalentcopper complexes, divalent ruthenium complexes, divalent iron complexesand divalent nickel complexes are exemplified. Among these, coppercomplexes are preferable.

Specific examples of the monovalent copper compound include cuprouschloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprousoxide, and cuprous perchlorate.

When the copper compound is used, a ligand such as 2,2′-bipyridyl or itsderivative, 1,10-phenanthroline or its derivative, or a polyamine suchas tetramethylethylenediamine, pentamethyldiethylenetriamine orhexamethyltris(2-aminoethyl)amine can be added in order to enhancecatalytic activity.

Further, tris(triphenylphosphine) complex (RuCl₂(PPh₃)₃) of divalentruthenium chloride is also preferable as a catalyst.

When the ruthenium compound is used as a catalyst, an aluminum alkoxidecan be added as an activating agent.

Further, bis(triphenylphosphine) complex (FeCl₂(PPh₃)₂) of divalentiron, bis(triphenylphosphine) complex (NiCl₂(PPh₃)₂) of divalent nickeland bis(tributylphosphine) complex (NiBr₂(PBu₃)₂) of divalent nickel arealso preferable as the catalyst.

The polymerization can be carried out without a solvent or in varioussolvents.

Examples of the solvent include hydrocarbon solvents such as benzene andtoluene; ether solvents such as diethyl ether and tetrahydrofuran;halogenated hydrocarbon solvents such as methylene chloride andchloroform; ketone solvents such as acetone, methyl ethyl ketone andmethyl isobutyl ketone; alcohol solvents such as methanol, ethanol,propanol, isopropanol, n-butanol and tert-butanol; nitrile solvents suchas acetonitrile, propionitrile and benzonitrile; ester solvents such asethyl acetate and butyl acetate; carbonate solvents such as ethylenecarbonate and propylene carbonate. These may be used alone or at least 2solvents may be used in mixture.

Further, the polymerization can be carried out in a range of roomtemperature to 200° C. and preferably 50° to 150° C.

<Method for Introduction of Functional Group>

The method for manufacturing components (A) and (B) is not specificallylimited, but for example, they can be produced by producing a vinylpolymer having a reactive functional group by the above-mentioned methodand converting the reactive functional group to a substitutent having a(meth)acryloyl group.

A method of converting the end of the vinyl polymer having a reactivefunctional group to a group represented by general formula (1) isdescribed below.

The method of introducing a (meth)acryloyl group to the end of the vinylpolymer is not specifically limited, but those mentioned below areexemplified.

(Introduction Method 1)

A method wherein a vinyl polymer having a halogen group at the end isreacted with a compound indicated by general formula (2):M⁺⁻OC(O)C(R^(a))═CH₂  (2)wherein R^(a) represents a hydrogen atom or an organic group having 1 to20 carbon atoms, and M⁺ represents an alkali metal ion or a quaternaryammonium ion).

As the vinyl polymer having a halogen group at the end, a vinyl polymerhaving an end group indicated by general formula (3):—CR¹R²X  (3)wherein R¹ and R² represent a group bonded to the ethylenicallyunsaturated group of a vinyl monomer, and X represents a chlorine atom,a bromine atom or an iodine atom, is preferable.(Introduction Method 2)

A method wherein a vinyl polymer having a hydroxyl group at the end isreacted with a compound indicated by general formula (4):X¹C(O)C(R^(a))═CH₂  (4)wherein R^(a) represents a hydrogen atom or an organic group having 1 to20 carbon atoms, and X¹ represents a chlorine atom, a bromine atom or ahydroxyl group.(Introduction Method 3)

A method wherein a vinyl polymer having a hydroxyl group at the end isreacted with a diisocyanate compound and the residual isocyanate groupis reacted with a compound indicated by general formula (5):HO—R′—OC(O)C(R^(a))═CH₂  (5)wherein R^(a) represents a hydrogen atom or an organic group having 1 to20 carbon atoms, and R′ represents a divalent organic group having 2 to20 carbon atoms.

The above-mentioned methods are specifically described below.

[Introduction Method 1]

The introduction method 1 is a method wherein a vinyl polymer having ahalogen group at the end is reacted with a compound indicated by generalformula (2).

The vinyl polymer having a halogen group at the end is not specificallylimited, but those having an end group indicated by general formula (3)are preferable.

The vinyl polymer having a halogen group at the end, in particular, thevinyl polymer having an end group indicated by general formula (3), isproduced by the method of polymerizing a vinyl monomer using theabove-mentioned organic halide or halogenated sulfonyl compound as aninitiator and the transition metal complex as a catalyst, or by themethod of polymerizing a vinyl monomer using a halogen compound as achain transfer agent, but the former is preferable.

The compound indicated by general formula (2) is not specificallylimited.

As the organic group having 1 to 20 carbon atoms in R^(a) in generalformula (2), those like the above-mentioned are exemplified and specificexamples like the above-mentioned are recited.

The M⁺ in general formula (2) is the counter cation of oxy anion andexamples thereof include alkali metal ions, quaternary ammonium ions.

Examples of the alkali metal ions include lithium ion, sodium ion, andpotassium ion, and examples of the quaternary ammonium ions includetetramethylammonium ion, tetraethylammonium ion, tetrabenzylammoniumion, trimethyldodecylammonium ion, tetrabutylammonium ion, anddimethylpiperidinium ion. Among these, alkali metal ions are preferableand sodium ion and potassium ion are more preferable.

The amount of the compound indicated by general formula (2) used ispreferably 1 to 5 equivalents based on the end group indicated bygeneral formula (3) and more preferably 1.0 to 1.2 equivalents.

The solvent used for carrying out the reaction is not specificallylimited, but a polar solvent is preferable because of nucleophilicdisplacement reaction. Preferable examples thereof includetetrahydrofuran, dioxane, diethyl ether, acetone, dimethylsulfoxide,dimethylformamide, dimethylacetoamide, hexamethylphosphoric triamide,and acetonitrile.

The reaction temperature is not specifically limited, but preferably 0°to 150° C. and more preferably 10° to 100° C.

[Introduction Method 2]

The introduction method 2 is a method wherein a vinyl polymer having ahydroxyl group at the end is reacted with a compound indicated bygeneral formula (4).

The compound indicated by general formula (4) is not specificallylimited.

As the organic group having 1 to 20 carbon atoms in R^(a) in generalformula (4), those like the above-mentioned are exemplified and specificexamples like the above-mentioned are recited.

The vinyl polymer having a hydroxyl group at the end is produced by themethod of polymerizing a vinyl monomer using the above-mentioned organichalide or halogenated sulfonyl compound as an initiator and thetransition metal complex as a catalyst, or by the method of polymerizinga vinyl monomer using a compound having a hydroxyl group as a chaintransfer agent, but the former is preferable.

The method of producing the vinyl polymer having a hydroxyl group at theend is not specifically limited, but for example, methods below areexemplified.

-   a) A method of reacting a compound having a polymerizable alkenyl    group and a hydroxyl group in combination in one molecule which is    indicated by general formula (10):    H₂C═C(R¹³)—R¹⁴—R¹⁵—OH  (10)-    wherein R¹³ represents a hydrogen atom or an organic group having 1    to 20 carbon atoms, R¹⁴ represents —C(O)O— (an ester group) or an    o-, m-, p-phenylene group, and R¹⁵ represents a direct bond or a    divalent organic group having 1 to 20 carbon atoms which may    optionally contain at least one ether bond, and the like, as the    second monomer when the vinyl polymer is synthesized by the living    radical polymerization.

The above-mentioned R¹³ is preferably a hydrogen atom or a methyl group.Those in which R¹⁴ is an ester group are (meth)acrylate compounds andthose in which R¹⁴ is a phenylene group are styrene compounds.

The timing at which the compound having a polymerizable alkenyl groupand a hydroxyl group in combination in one molecule is reacted is notspecifically limited, but when rubbery nature is expected in particular,it is preferably reacted as the second monomer at the time oftermination of the polymerization reaction or after completion of thereaction of a given monomer.

-   b) A method of reacting a compound having a less polymerizable    alkenyl group and a hydroxyl group in combination in one molecule as    the second monomer at the time of termination of the polymerization    reaction or after completion of the reaction of a given monomer when    the vinyl polymer is synthesized by the living radical    polymerization.

Such a compound is not specifically limited, but examples thereofinclude compounds indicated by general formula (11):H₂C═C(R¹³)—R¹⁶—OH  (11)wherein R¹³ is the same as the above-mentioned and R¹⁶ represents adivalent organic group having 1 to 20 carbon atoms which may optionallyhave at least one ether bond.

The compounds indicated by general formula (11) are not specificallylimited, but alkenyl alcohols such as 10-undecenol, 5-hexenol and allylalcohol are preferable from the viewpoint of easy availability.

-   c) A method of introducing a hydroxyl group at the end by    hydrolyzing the halogen atom of the vinyl polymer having at least    one carbon-halogen bond indicated by general formula (3) which is    obtained by the atom transfer radical polymerization, or by reacting    the halogen atom of the vinyl polymer with a compound containing a    hydroxyl group, according to such a method as disclosed in    JP-A-4-132706.-   d) A method of substituting halogen by reacting stabilized carbanion    having a hydroxyl group which is indicated by general formula (12):    M⁺C⁻(R¹⁷)(R¹⁸)—R¹⁶—OH  (12)-    wherein R¹⁶ and M⁺ are the same as the above-mentioned and both of    R¹⁷ and R¹⁸ are an electron attractive group stabilizing the    carbanion C⁻ or either of them is the electron attractive group and    the other is a hydrogen atom, an alkyl group having 1 to 10 carbon    atoms or a phenyl group, with a vinyl polymer having at least one    carbon-halogen bond indicated by general formula (3) which is    obtained by the atom transfer radical polymerization.

Examples of the electron attractive group include —CO₂R (ester group),—C(O)R (keto group), —CON(R)₂ (amide group), —COSR (thioester group),—CN (nitrile group), and —NO₂ (nitro group), and —CO₂R, —C(O)R and —CNare preferable in particular. The substitutent R is an alkyl grouphaving 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atomsor an aralkyl group having 7 to 20 carbon atoms and preferably an alkylgroup having 1 to 10 carbon atoms or a phenyl group.

-   e) A method of acting a simple metal such as zinc or an    organometallic compound on a vinyl polymer having at least one    carbon-halogen bond indicated by general formula (3) which is    obtained by the atom transfer radical polymerization, preparing    enolate anion and then reacting an aldehyde or ketone therewith.-   f) A method of reacting a hydroxyl group containing compound    represented by general formula (13):    HO—R¹⁶—O⁻M⁺  (13)-    wherein R¹⁶ and M⁺ are the same as the above-mentioned, or a    hydroxyl group containing compound indicated by general formula    (14):    HO—R¹⁶—C(O)O⁻M⁺  (14)    wherein R¹⁶ and M⁺ are the same as the above-mentioned, with a vinyl    polymer having at least one halogen atom at the polymer terminal,    preferably halogen atom indicated by general formula (3), and    substituting the above-mentioned halogen atom with a hydroxyl group    containing substitutent.

When a halogen atom does not participate in the method introducing ahydroxyl group like methods (a) and (b), method (b) is more preferablebecause the control is easier.

When a hydroxyl group is introduced by converting the halogen atom ofthe vinyl polymer having at least one carbon-halogen bond like methods(c) to (f) method (f) is more preferable because the control is easier.

The amount of the compound indicated by general formula (4) used ispreferably 1 to 10 equivalents based on the end hydroxyl group of thevinyl polymer and more preferably 1 to 5 equivalents.

The solvent used for carrying out the reaction is not specificallylimited, but a polar solvent is preferable because of nucleophilicdisplacement reaction. Preferable examples thereof includetetrahydrofuran, dioxane, diethyl ether, acetone, dimethylsulfoxide,dimethylformamide, dimethylacetoamide, hexamethylphosphoric triamide,and acetonitrile.

The reaction temperature is not specifically limited, but preferably 0°to 150° C. and more preferably 10° to 100° C.

(Introduction Method 3)

A method wherein a vinyl polymer having a hydroxyl group at the end isreacted with a diisocyanate compound and the residual isocyanate groupis reacted with a compound indicated by general formula (5):HO—R′—OC(O)C(R^(a))═CH₂  (5)wherein R^(a) represents a hydrogen atom or an organic group having 1 to20 carbon atoms, and R′ represents a divalent organic group having 2 to20 carbon atoms.

As the organic group having 1 to 20 carbon atoms in R^(a) in generalformula (5), those like the above-mentioned are exemplified and specificexamples like the above-mentioned are recited.

Examples of the divalent organic group having 2 to 20 carbon atomsindicated by R′ in general formula (5) include alkylene groups having 2to 20 carbon atoms (an ethylene group, a propylene group, a butylenegroup and the like), alkylene groups having 6 to 20 carbon atoms, andalkylene groups having 7 to 20 carbon atoms.

The compound indicated by general formula (5) is not specificallylimited, but specifically preferable compounds are 2-hydroxypropylmethacrylate, and the like.

The vinyl polymer having a hydroxyl group at the end is mentioned above.

The diisocyanate compound is not specifically limited and any of thosewhich have been conventionally known can be used. Specific examplesthereof include tolylene diisocyanate, 4,4′-diphenylmethanediisocyanate, hexamethylene diisocyanate, xylylene diisocyanate,m-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenateddiphenylmethane diisocyanate hydrogenated tolylene diisocyanate,hydrogenated xylylene diisocyanate, and isophorone diisocyanate. Thesemay be used alone or 2 or more of them may be used in combination.Further, blocked isocyanates may be used. Diisocyanate compounds havingno aromatic ring such as hexamethylene diisocyanate and hydrogenateddiphenylmethane diisocyanate are preferably used to obtain moresatisfactory weather resistance.

The amount of the diisocyanate compound used is preferably 1 to 10equivalents based on the end hydroxyl group of the vinyl polymer andmore preferably 1 to 5 equivalents.

The reaction solvent is not specifically limited, but aprotic solventand the like are preferable.

The reaction temperature is not specifically limited, but preferably 0°to 250° C. and more preferably 20° to 200° C.

The amount of the compound indicated by general formula (5) used ispreferably 1 to 10 equivalents based on the residual isocyanate groupand more preferably 1 to 5 equivalents.

<Active Energy Curing Type Composition for In-Place Shaping Gasket>

The composition for in-place shaping gasket of the present inventioncomprises components (A) and (B) as essential components, wherein theviscosity of the composition is 400 Pa·s or less at 23° C., preferably300 Pa·s or less at 23° C. and the compression set (obtained by aprocedure wherein strain after compressed by 25% at 150° C. for 70 hoursis measured and the strain which is not restored after the release ofcompression is expressed in terms of percentage, provided that thequantity of compression applied is 100%) of a cured article which isprescribed in JIS K 6262 is 30% or less.

When the viscosity of the composition is higher than 400 Pa·s at 23° C.,workability is remarkably lowered when the coating of the composition ona substrate is carried out. Further, since heat resistance and sealproperty are required for an in-place shaping gasket, the compressionset determined under the above-mentioned conditions is preferably 30% orless. A polymerizable monomer and/or oligomer or various additives canbe optionally used in combination, besides component (B) for the purposeof the improvement of surface curability, the addition of toughness orthe improvement of workability due to reduction of viscosity.

As the above-mentioned polymerizable monomer and/or oligomer, a monomerand/or oligomer having a radical polymerizable group, or a monomerand/or oligomer having an anion polymerizable group is preferable fromthe viewpoint of reactivity.

Examples of the radical polymerizable group include a (meth)acryloylgroup such as a (meth)acrylic group, a styrene group, an acrylonitrilegroup, a vinyl ester group, an N-vinyl pyrrolidone group, an acrylamidegroup, a conjugated diene group, a vinyl ketone group, and a vinylchloride group. Among these, those having a (meth)acrylic group whichare similar to the polymer used in the present invention are preferable.

Examples of the anion polymerizable group include a (meth)acryloyl groupsuch as a (meth)acrylic group, a styrene group, an acrylonitrile group,an N-vinyl pyrrolidone group, an acrylamide group, a conjugated dienegroup, and a vinyl ketone group. Among these, those having a(meth)acryloyl group which are similar to the polymer used in thepresent invention are preferable.

Specific examples of the monomer include a (meth)acrylate monomer, acyclic acrylate, N-vinyl pyrrolidone, styrene monomer, acrylonitrile,N-vinyl pyrrolidone, acrylamide monomer, a conjugated diene monomer, avinyl ketone monomer, and a polyfunctional monomer.

Examples of the (meth)acrylate monomer include methyl (meth)acrylate,ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl (meth)acrylate,n-butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate,n-pentyl(meth)acrylate, n-hexyl (meth)acrylate,cyclohexyl(meth)acrylate, n-heptyl(meth)acrylate, n-octyl(meth)acrylate,isooctyl(meth)acrylate, 2-ethylhexyl (meth)acrylate,nonyl(meth)acrylate, isononyl(meth)acrylate, decyl (meth)acrylate,dodecyl(meth)acrylate, phenyl(meth)acrylate, tolyl (meth)acrylate,benzyl(meth)acrylate, 2-methoxyethyl(meth)acrylate,3-methoxybutyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate, stearyl(meth)acrylate, glycidyl(meth)acrylate, 2-aminoethyl(meth)acrylate,γ-(methacryloyloxy)propyltrimethoxysilane, an ethylene oxide adduct of(meth)acrylic acid, trifluoromethylmethyl(meth)acrylate,2-trifluoromethylethyl(meth)acrylate, 2-perfluoroethylethyl(meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl(meth)acrylate,2-perfluoroethyl(meth)acrylate, perfluoromethyl(meth)acrylate,di-perfluoromethylmethyl(meth)acrylate,2-perfluoromethyl-2-perfluoroethylethyl(meth)acrylate,2-perfluorohexylethyl(meth)acrylate, 2-perfluorodecylethyl(meth)acrylate, and 2-perfluorohexadecylethyl(meth)acrylate. Further,compounds indicated by the formulae below can be exemplified. Herein, nindicates an integer of 0 to 20 in the formulae below.

The styrene monomers include styrene, α-methylstyrene and the like; theacrylamide monomers include acrylamide, N,N-dimethylacrylamide and thelike; the conjugated diene monomers include butadiene, isoprene and thelike; and the vinyl ketone monomers include methyl vinyl ketone and thelike.

Examples of the polyfunctional monomer include trimethylolpropanetriacrylate, neopentylglycol polypropoxy diacrylate,trimethylolpropanepolyethoxy triacrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxy diacrylate, dipentaerythritolpolyhexanolide hexaacrylate, tris(hydroxyethyl)isocyanuratepolyhexanolide triacrylate, tricyclodecanedimethylol diacrylate,2-(2-acryloyloxy-1,1-dimethyl)-5-ethyl-5-acryloyloxymethyl-1,3-dioxane,tetrabromobisphenol A diethoxy diacrylate, 4,4-dimercaptodiphenylsulfidedimethacrylate, polytetraethylene glycol diacrylate, 1,9-nonanedioldiacrylate, and ditrimethylolpropane tetraacrylate.

Examples of the oligomer include epoxy acrylate resins such as abisphenol A type epoxy acrylate resin, a phenolnovolac type epoxyacrylate resin and a cresol novolac type epoxy acrylate resin; a COOHmodified epoxy acrylate resin; urethane acrylate resins obtained byreacting a urethane resin obtained from a polyol (polytetramethyleneglycol, polyester diol from ethylene glycol and adipic acid,ε-caprolactone modified polyester diol, polypropylene glycol,polyethylene glycol, polycarbonate diol, hydrogenated polyisoprene withend hydroxy group, polybutadiene with end hydroxy group, polyisobutylenewith end hydroxy group, and the like) and an organic isocyanate(tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and thelike), with (meth)acrylate containing a hydroxy group(hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate,hydroxybutyl(meth)acrylate, pentaerythritol triacrylate, and the like);resins in which a (meth)acrylic group is introduced into theabove-mentioned polyol through ester bond; polyester acrylate resins.

The number average molecular weight of the monomer and/or oligomerhaving a (meth)acryloyl group is preferably 5,000 or less. When themonomer is used for the reduction of viscosity to improve surfacecurability and workability, the molecular weight thereof is morepreferably 1,000 or less because satisfactory compatibility.

As the organic solvent, solvents with a boiling point of 50° to 180° C.are preferable because workability on coating and drying property beforeand after curing are superior. Specific examples thereof include alcoholsolvents such as methanol, ethanol, isopropanol, n-butanol andisobutanol; ester solvents such as methyl acetate, ethyl acetate, butylacetate, ethylene glycol monoethyl ether, ethylene glycol monoethylether acetate and ethylene glycol monobutyl ether; ketone solvents suchas acetone, methyl ethyl ketone and methyl isobutyl ketone; aromaticsolvents such as toluene and xylene; and cyclic ethers such as dioxane.These solvents may be used alone or 2 or more of them may be used inmixture.

For the composition for an in-place shaping gasket of the presentinvention, it is useful to add reinforcing silica from the viewpoint ofthe improvement of strength of cured product.

Examples of the reinforcing silica include fumed silica and precipitatedsilica. Among these, silica with a particle size of 50 μm or less and aspecific area of 80 m²/g or more is preferable from the viewpoint of theeffect of reinforcement.

Further, surface-treated silica, for example, silica surface-treatedwith organosilane, organosilazane, diorganocyclopolysiloxane or thelike, is more preferable because flowability suitable for shaping iseasily realized.

Specific examples of the reinforcing silica is not specifically limited,but include AEROSIL manufactured by Nippon Aerosil Co. which is one offumed silica, and Nipsil manufactured by Nippon Silica Industrial Co.Ltd. which is one of precipitated silica.

The reinforcing silica may be used alone and 2 or more of them may beused in combination.

The addition amount of the reinforcing silica is not specificallylimited, but is preferably from 0.1 to 100 parts, more preferably from0.5 to 80 parts and most preferably from 1 to 50 parts, based on 100parts of the total of components (A) and (B). When the amount is lessthan 0.1 part, the improvement effect of reinforcing property isoccasionally inadequate. When the amount exceeds 100 parts, theworkability of the composition is occasionally lowered.

Various fillers may be used for the composition of the present inventionif necessary, in addition to the reinforcing silica.

Examples of the fillers are not specifically limited, but includereinforcing fillers such as wood flour, pulp, cotton chip, asbestos,glass fiber, carbon fiber, mica, walnut shell powder, rice husk shellpowder, graphite, diatom earth, white earth, dolomite, silicicanhydride, hydrated silicic acid and carbon black; filling agents suchas heavy calcium carbonate, colloidal calcium carbonate, magnesiumcarbonate, diatom earth, calcined clay, clay, talc, titanium oxide,bentonite, organic bentonite, ferric oxide, red iron oxide, aluminumfine powder, flint powder, zinc oxide, active zinc oxide, zinc powder,zinc carbonate and Shirasu balloon; fibrous filling agents such asasbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber andpolyethylene fiber. Among these filling agents, carbon black, calciumcarbonate, titanium oxide, talc and the like are preferable. Further,when a cured article with low strength and large elongation is desired,filling agents mainly selected from titanium oxide, calcium carbonate,talc, ferric oxide, zinc oxide, Shirasu balloon and the like can beadded.

When the specific surface area of calcium carbonate is small, theimprovement effects of strength at break, elongation at break andadhesiveness and weather resistant adhesiveness of the cured article areoccasionally inadequate in general. The larger the value of the specificsurface area, the greater the improvement effects of strength at break,elongation at break and adhesiveness and weather resistant adhesivenessof the cured article are. As calcium carbonate, those surface-treatedusing a surface treating agent are preferably used. When surface-treatedcalcium carbonate is used, it is considered that the workability of thecomposition of present invention is improved and the improvement effectsof adhesiveness and weather resistant adhesiveness of the curablecomposition is further improved, as compared to calcium carbonate whichis not surface-treated.

As the surface treating agents, organic substances such as fatty acid,fatty acid soap and fatty acid ester, and various surfactants, variouscoupling agents such as a silane coupling agent and a titanate couplingagent are used. Specific examples thereof include, not limited to these,fatty acids such as caproic acid, caprylic acid, pelargonic acid, capricacid, undecanoic acid, lauric acid, myristic acid, palmitic acid,stearic acid, behenic acid and oleic acid; and sodium salts andpotassium salts of those fatty acids, and alkyl esters of those fattyacids. Specific examples of the surfactant include sulfate type anionsurfactants such as sodium salts and potassium salts of polyoxyethylenealkyl ether sulfate and long chain alcohol sulfates; sulfonic acid typeanion surfactants such as sodium salts and potassium salts ofalkylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, paraffinsulfonic acid, α-olefin sulfonic acid and alkyl sulfosuccinic acid.

The amount of the surface treating agent used is preferably in a rangeof 0.1 to 20%, more preferably in a range of 1 to 5%, based on calciumcarbonate. When the amount is less than 0.1%, the improvement effects ofworkability and adhesiveness and weather resistant adhesiveness are notoccasionally adequate. When the amount exceeds 20%, the storagestability of the composition is occasionally lowered.

When calcium carbonate is used, the type thereof is not specificallylimited, but colloidal calcium carbonate is preferably used when theimprovement effects of the thixotropy of the composition and thestrength at break, elongation at break, adhesiveness and weatherresistant adhesiveness of a cured article and the like are especiallyexpected.

On the other hand, heavy calcium carbonate is occasionally added forreducing the viscosity of the composition, increasing the quantity ofthe composition and lowering cost. When heavy calcium carbonate is used,those described below can be used according to requirement.

The heavy calcium carbonate means that obtained by mechanicallypulverizing and processing natural chalk, marble stone, lime stone orthe like. Pulverization process includes a wet process and a dryprocess, but a wet pulverization product is often not preferable becausethe storage stability of the composition of the present invention isoften deteriorated. Sieving of heavy calcium carbonate gives productshaving various average particle sizes. The specific surface area ofcalcium carbonate is not specifically limited, but when the improvementeffects of the strength at break, elongation at break, adhesiveness andweather resistant adhesiveness of a cured article are expected, thespecific surface area is preferably at least 1.5 m²/g and at most 50m²/g, more preferably at least 2 m²/g and at most 50 m²/g, further morepreferably at least 2.4 m²/g and at most 50 m²/g and most preferably atleast 3 m²/g and at most 50 m²/g. When the specific surface area is lessthan 1.5 m²/g, the improvement effects are occasionally inadequate. Ofcourse, when the viscosity is merely reduced and the purpose is only toincrease the quantity of the composition, the specific surface area isnot limited.

The specific surface area means a measurement obtained by an airpermeation method (a method of determining the specific surface areafrom the degree of permeation of air through powder filling layer) whichis carried out according to JIS K 5101 as a measuring method. As themeasuring device, a specific surface area measuring device SS-100manufactured by Shimadzu Corporation is preferably used.

These filling agents may be used alone or 2 or more of them may be alsoused in combination according to purpose and requirement. Thecombination is not specifically limited, but, for example, when heavycalcium carbonate with a specific surface area of at least 1.5 m²/g andcolloidal calcium carbonate are used in combination, the increase ofviscosity of the composition is suppressed to a certain degree and theimprovement effects of the strength at break, elongation at break,adhesiveness and weather resistant adhesiveness of a cured article canbe greatly expected.

When the filling agent is used, the amount of the filling agent ispreferably in a range of 5 to 1,000 parts, more preferably in a range of20 to 500 parts and most preferably in a range of 40 to 300 parts, basedon 100 parts of the total of components (A) and (B). When the amount isless than 5 parts, the improvement effects of the strength at break,elongation at break, adhesiveness and weather resistant adhesiveness ofa cured article are occasionally inadequate and when it exceeds 1,000parts, the workability of the composition is occasionally lowered. Thefilling agent may be used alone or at least 2 thereof may be used incombination.

Since the composition for an in-place shaping gasket of the presentinvention comprises preferably (meth)acrylic polymers as a maincomponent, the addition of a tackifier resin is not always necessary,but various kinds of tackifier resins can be used if necessary. Specificexamples thereof include a phenol resin, a modified phenol resin, acyclopentadiene-phenol resin, a xylene resin, a coumarone resin, apetroleum resin, a terpene resin, a terpene-phenol resin, and a rosinester resin.

Various additives such as an anti-aging agent, a plasticizer, a physicalproperty modifier and a solvent may be added to modify physicalproperties for the composition for an in-place shaping gasket of thepresent invention.

Since the acrylic polymer is a polymer naturally superior in heatresistance, weather resistance and durability, an anti-aging agent isnot always necessary, but a conventionally known antioxidant or a lightstabilizer can be suitably used. Further, the anti-aging agent can bealso used for polymerization control at polymerization and the controlof physical properties. As the antioxidant, various kinds have beenknown and those described in “Antioxidant Handbook” published byTaiseisya Ltd., “Degradation and Stabilization of Polymer Material” (235to 242) published by CMC Books Co. and the like are exemplified, but theantioxidant to be used in the present invention is not specificallylimited to these. Examples thereof include thio ethers such as MARKPEP-36 and MARK AO-23 (both above are manufactured by Adeka ArgusChemical Co., Ltd.), phosphorous antioxidants such as Irgafos 38,Irgafos 168 and Irgafos P-EPQ (all above are manufactured by Chiba-GeigyJapan Ltd.). Among these, hindered phenol compounds shown below arepreferable. Specific examples of the hindered phenol compounds belowinclude 2,6-di-tert-butyl-4-methylphenol,2,6-di-tert-butyl-4-ethylphenol, mono(or di ortri)(α-methylbenzyl)phenol,2,2′-methylenebis(4-ethyl-6-tert-butylphenol),2,2′-methylenebis(4-methyl-6-tert-butylphenol),4,4′-butylidenebis(3-methyl-6-tert-butylphenol),4,4′-thiobis(3-methyl-6-tert-butylphenol),2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethyleneglycol bis-[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate],1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine,pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate],2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide),diethyl (3,5-di-tert-butyl-4-hydroxy-benzylphosphonate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylsulfonate),tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,4-2,4-bis[(octylthio)methyl]o-cresol,N,N′-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine,tris(2,4-di-tert-butylphenyl)phosphite,2-(5-methyl-2-hydroxyphenyl)benzotriazole,2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl)-2H-benzotriazole,2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole,2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole,2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole,2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole, a condensate ofmethyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionatewith polyethylene glycol (molecular weight: about 300),hydroxyphenylbenzotriazole derivative,bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di-tert-butyl-2-hydroxybenzyl)-2-n-butylmalonate, and2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

By referring to trade names, there can be exemplified NOCRAC 200, NOCRACM-17, NOCRAC SP, NOCRAC SP-N, NOCRAC NS-5, NOCRAC NS-6, NOCRAC NS-30,NOCRAC 300, NOCRAC NS-7 and NOCRAC DAH (all above manufactured byOUCHISHINKO CHEMICAL INDUSTRIAL CO., LTD.), MARK AO-30, MARK AO-40, MARKAO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO-80,MARK AO-15, MARK AO-18, MARK 328 and MARK AO-37 (all above manufacturedby Adeka Argus Chemical CO., LTD.), IRGANOX-245, IRGANOX-259,IRGANOX-565, IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076,IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330 andIRGANOX-1425WL (all above manufactured by Chiba-Geigy Japan Co., Ltd.),SUMILIZER GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) and thelike, but those to be used in the present invention are not limited tothese. Further, mono acrylate-phenol antioxidants having an acrylategroup and a phenol group in combination, nitroxide compounds and thelike are exemplified. Examples of the mono acrylate-phenol antioxidantinclude2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate (trade name: SUMILIZER GM),2,4-di-tert-amyl-6-[1-(3,5-di-tert-amyl-2-hydroxyphenyl)ethyl]phenylacrylate (trade name: SUMILIZER GS). The nitroxide compound is notlimited, but nitroxy free radicals from cyclic hydroxyamines, such as2,2,6,6-substituted-1-piperidinyloxy radical and2,2,5,5-substituted-1-pyrroridinyloxy radical, are exemplified. As thesubstitutent, alkyl groups having at most 4 carbon atoms such as amethyl group and an ethyl group are suitable. Specific examples of thenitroxy free radical compound is not limited, but include2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO),2,2,6,6-tetraethyl-1-piperidinyloxy radical,2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical,2,2,5,5-tetramethyl-1-pyrroridinyloxy radical,1,1,3,3-tetramethyl-2-isoindolinyloxy radical, and N,N-di-t-butylaminoxyradical. Stable free radical such as galvinoxyl free radical may be usedin place of the nitroxy free radical. The antioxidant may be used incombination with a light stabilizer and the combination use isespecially preferable because its effect is further exhibited andthereby heat resistance is occasionally improved in particular. TINUVINC353, TINUVIN B75 (all above manufactured by Chiba Geigy Japan Co.,Ltd.) and the like in which an antioxidant and a light stabilizer havebeen preliminarily mixed may be used.

Examples of the plasticizer include phthalic acid esters such as dibutylphthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate and butylbenzyl phthalate; non aromatic dibasic acid esters such as dioctyladipate and dioctyl sebacate; polyalkylene glycol esters such asdiethylene glycol dibenzoate and triethylene glycol dibenzoate;phosphoric acid esters such as tricresyl phosphate and tributylphosphate; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyland partially hydrogenated terphenyl. These may be used alone or 2 ormore of them can be used in mixture depending on purpose such as theadjustment of physical properties and the adjustment of characteristicproperties, but they are not always necessary. Further, theseplasticizers can be added at the time of production of the polymer.

Examples of the solvent which may be used in production of the polymerinclude aromatic hydrocarbon solvents such as toluene and xylene; estersolvents such as ethyl acetate, butyl acetate, amyl acetate andCellosolve acetate; ketone solvents such as methyl ethyl ketone, methylisobutyl ketone and di-isobutyl ketone.

Various adhesiveness modifiers may be added to the composition for anin-place shaping gasket of the present invention in order to improveadhesiveness to various supports (plastic film and the like). Examplesthereof include alkylalkoxysilanes such as methyltrimethoxysilane,dimethyldimethoxysilane, trimethylmethoxysilane andn-propyltrimethoxysilane; alkylisopropenoxysilane such asdimethyldiisopropenoxysilane, methyltriisopropenoxysilane andγ-glycidoxypropylmethyldiisopropenoxysilane; alkoxysilanes having afunctional group such as γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane,vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane,N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane,γ-mercaptopropyltrimethoxysilane andγ-mercaptopropylmethyldimethoxysilane; silicone varnishes; andpolysiloxanes.

<Curing Method>

The composition for an in-place shaping gasket in accordance with thepresent invention is cured by active energy radiation such as UV orelectron beam, or active energy such as heat. Curing by active energyradiation such as UV or electron beam is preferable for obtainingsatisfactory curability and compression set.

<Curing by Active Energy Radiation>

When the composition is cured by active energy radiation, thecomposition for an in-place shaping gasket preferably contains aphotopolymerization initiator.

The photopolymerization initiator of component (C) is not specificallylimited, but radical photoinitiator and anion photoinitiator arepreferable and the radical photoinitiator is preferable in particular.Examples thereof include acetophenone, propiophenone, benzophenone,xanthol, fluorlein, benzaldehyde, anthraquinone, triphenylamine,carbazole, 3-methylacetophenone, 4-methylacetophenone,3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone,3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene,3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone,4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone,3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone,benzoyl, benzoin methyl ether, benzoin butyl ether,bis(4-dimethylaminophenyl) ketone, benzyl methoxy ketal,2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethan-1-on,1-hydroxycyclohexyl phenyl ketone,2-hydroxy-2-methyl-1-phenyl-propan-1-one,2-methyl-1-[4-(methylthiophenyl)]-2-morpholinopropan-1-one, and2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1. Theseinitiators may be used alone or may be used in combination with othercompound. Specifically, examples of the combination include ancombination with an amine such as diethanol/methylamine,dimethylethanolamine or triethanolamine; an combination with an iodoniumsalt such as diphenyliodonium chloride in addition to the foregoingcombination; an combination with a dye such as methylene blue and anamine, and the like.

Further, when the photopolymerization initiator is used, apolymerization inhibitor such as hydroquinone, hydroquinone monomethylether, benzoquinone or para-tertiary-butylcathecol can be added ifnecessary.

Further, as a near infrared photopolymerization initiator, a nearinfrared absorptive cation dye may be used.

Preferable examples of the near infrared absorptive cation dye includethose which are excited by light energy in a range of 650 to 1,500 nm,for example, near infrared absorptive cation dye-borate anion complexdisclosed in JP-A-3-111402, JP-A-5-194619 and the like. This complex isfurther preferably used in combination with a boron sensitizer.

Since the amount of the photopolymerization initiator used is enough tooptically functionalize the system slightly, it is not specificallylimited, but is preferably 0.001 to 10 parts based on 100 parts of thetotal of components (A) and (B).

The active energy radiation source is not specifically limited, butexamples thereof include irradiation with light, electron beam and thelike, using a high pressure mercury lamp, a low pressure mercury lamp,an electron beam irradiation device, a halogen lamp, a light emittingdiode, a semiconductor laser, and the like in accordance with the natureof the photopolymerization initiator.

<In-Place Shaping Gasket>

With respect to the in-place shaped gasket which is obtained by curingthe composition for in-place shaping gasket in accordance with thepresent invention with active energy in place, the compression set ofthe cured article prescribed in JIS K 6262 is preferably at most 30%,more preferably at most 20%, further more preferably at most 15%, mostpreferably at most 10%, for adequately satisfying requisite heatresistance and seal property.

The compression set in the present invention is a value obtained by theprocedure wherein strain of cured article after compressed by 25% at150° C. for 70 hours is measured and the strain which is not restoredafter release of the compression is expressed in terms of percentage,provided that the quantity of compression applied is 100%. Thecompression set is specifically measured by the procedure below.

(1) The cured article is maintained at 150° C. for 70 hours in a statewhere it is deformed by 25% compression.

(2) The load for causing compression deformation is removed; temperatureat release: 23° C., release time: for 0.5 hour.

(3) The cured article released from the compression is going to returnto its original form before the compression (restored).

The compression set represents the deformation remaining after removingthe load causing compression deformation in terms of percentage. Namely,when the form of the cured article after release from the compression isthe form deformed by the compression before release as it is, thecompression set is 100%. On the other hand, when the cured articlereturns completely to the original form before the compression, thecompression set is 0%.

The in-place shaping gasket is preferably used for seal at a site whereoil resistance, or oil resistance and heat resistance are required, sealaround the engine of automobiles, the seal of the oil pan joint face ofautomobiles, and the like.

The oil resistance of the in-place shaped gasket shall preferably exceedthe oil resistance of the cured article of a composition comprising apolymer in which the repeating unit of vinyl polymer main chains ofcomponents (A) and (B) is changed to butyl acrylate alone, with respectto at least one of items of the immersion test of JIS K 6258 forlubricating oil Class 3 No. 5 for road vehicle prescribed in JIS K 2215.Further, a mass change ratio after to before immersion shall bepreferably at most 50%, in the immersion test of JIS K 6258 forlubricating oil Class 3 No. 5 for road vehicle prescribed in JIS K 2215.Furthermore, mass change ratio after to before immersion shall bepreferably smaller than that of the cured article of a compositioncomprising a polymer in which the repeating unit of vinyl polymer mainchains of components (A) and (B) is changed to butyl acrylate alone, inthe immersion test of JIS K 6258 for lubricating oil Class 3 No. 5 forroad vehicle prescribed in JIS K 2215. Further, volume change ratioafter to before immersion shall be preferably smaller than that of thecured article of a composition comprising a polymer in which therepeating unit of vinyl polymer main chains of components (A) and (B) ischanged to butyl acrylate alone, in the immersion test of JIS K 6258 forlubricating oil Class 3 No. 5 for road vehicle prescribed in JIS K 2215.

BEST MODE FOR CARRYING OUT THE INVENTION

The composition for an in-place shaping gasket in accordance with thepresent invention is characterized by comprising the under-mentionedcomponents (A) and (B) as essential components, wherein the viscosity ofthe composition is 400 Pa·s or less at 23° C. and the compression set(obtained by a procedure wherein strain after compressed by 25% at 150°C. for 70 hours is measured and the strain which is not restored afterthe release of compression is expressed in terms of percentage, providedthat the quantity of compression applied is 100%) of a cured articlewhich is prescribed in JIS K 6262 is 30% or less.

(A) a vinyl polymer having two or more groups represented by generalformula (1):—OC(O)C(R^(a))═CH₂  (1)wherein R^(a) represents a hydrogen atom or an organic group having 1 to20 carbon atoms, per molecule at the molecular ends.

(B) a vinyl polymer having one group represented by general formula (1)per molecule at the molecular end.

The respective polymers of components (A) and (B) are acrylic acid esterpolymers and their main chain is preferably that prepared by the livingradical polymerization and more preferably by the atom transfer radicalpolymerization. Further, the addition of a photopolymerization initiator(C) is preferable in addition to components (A) and (B). Further, theaddition of an acrylate monomer is effective from the viewpoints of theimprovement of strength, the addition of elongation and the improvementof workability and the like of the cured article. The composition for anin-place shaping gasket in accordance with the present invention ispreferably cured by active energy radiation such as UV or electron beamfor achieving satisfactory curability and compression set.

EXAMPLES

The specific Examples of the present invention are illustrated incombination with Comparative Examples, but the present invention is notlimited to the under-mentioned Examples.

In the under-mentioned Examples, the number average molecular weight andthe molecular weight distribution (the ratio of weight average molecularweight to number average molecular weight) were determined by a standardpolystyrene conversion method using gel permeation chromatography (GPC).A column in which crosslinked polystyrene gel was packed (Shodex GPCK-804 manufactured by Showa Denko K. K.) was used as a GPC column andchloroform was used as GPC solvent.

In the under-mentioned Examples, the average number of a terminal(meth)acryloyl group is the number of the (meth)acryloyl groupintroduced per one molecule of the polymer and determined based on thenumber average molecular weight determined by ¹H NMR analysis and GPC.

Production Example 1 Synthesis of poly(n-butyl acrylate/ethylacrylate/2-methoxyethyl acrylate) Having Acryloyl Groups at Both Ends

N-butyl acrylate/ethyl acrylate/2-methoxyethyl acrylate were polymerizedat a ratio of 25/46/29 by mole using cuprous bromide as a catalyst,pentamethyldiethylenetriamine as a ligand and diethyl 2,5-dibromoadipateas an initiator to obtain poly(n-butyl acrylate/ethylacrylate/2-methoxyethyl acrylate) having a number average molecularweight of 16,500, a molecular weight distribution of 1.13 and brominegroups at its ends.

400 g of the polymer was dissolved in N,N-dimethylacetoamide (400 ml),10.7 g of potassium acrylate was added and the mixture was heated withstirring at 70° C. for 6 hours under nitrogen atmosphere to obtain amixture composed of poly(n-butyl acrylate/ethyl acrylate/2-methoxyethylacrylate) having acryloyl groups at both ends (hereinafter referred toas polymer [1]). After the N,N-dimethylacetoamide in the mix solutionwas removed under reduced pressure, toluene was added to the residue andthe insoluble portion was removed by filtration. The toluene in thefiltrate was removed under reduced pressure to give a purified polymer[1].

With respect to polymer [1] having acryloyl groups at both ends afterpurification, the number average molecular weight was 16,900, themolecular weight distribution was 1.14 and the average number of endacryloyl group was 1.8 (namely, the introduction percentage of theacryloyl group to ends was 90%).

Production Example 2 Synthesis of poly(n-butyl acrylate/ethylacrylate/2-methoxyethyl acrylate) having acryloyl group at one end

N-butyl acrylate/ethyl acrylate/2-methoxyethyl acrylate were polymerizedat a ratio of 25/46/29 by mole using cuprous bromide as a catalyst,pentamethyldiethylenetriamine as a ligand and ethyl 2-bromobutyrate asan initiator to obtain poly(n-butyl acrylate/ethylacrylate/2-methoxyethyl acrylate) having a number average molecularweight of 3,700, a molecular weight distribution of 1.14 and a brominegroup at one end.

1,050 g of the polymer was dissolved in N,N-dimethylacetoamide (1,050g), 56.2 g of potassium acrylate was added and the mixture was heatedwith stirring at 70° C. for 4 hours under nitrogen atmosphere to obtaina mixture composed of poly(n-butyl acrylate/ethylacrylate/2-methoxyethyl acrylate) having an acryloyl group at one end(hereinafter referred to as polymer [2]). After theN,N-dimethylacetoamide in the mix solution was removed under reducedpressure, toluene was added to the residue and the insoluble portion wasremoved by filtration. The toluene in the filtrate was removed underreduced pressure to give a purified polymer [2].

With respect to polymer [2] having an acryloyl group at one end afterpurification, the number average molecular weight was 3,800, themolecular weight distribution was 1.15 and the average number of endacryloyl group was 1.0 (namely, the introduction percentage of theacryloyl group to one end was nearly 100%).

Example 1

0.22 Part of 2,2-diethoxyacetophenone and 1.1 parts of Irganox 1010(manufactured by Chiba Specialty Chemicals Co., Ltd.) were added to 100parts of polymer [1] obtained in Production Example 1 and 10 parts ofpolymer [2] obtained in Production Example 2 and the mixture wasadequately mixed to obtain a curable composition. The viscosity at roomtemperature (23° C.) of the composition was 370 Pa·s.

Then, the curable composition obtained was passed 3 times under a metalhalide lamp (80 W/cm, an irradiation distance of 15 cm and a belt speedof 1.0 m/min) for light irradiation to obtain a sheet shaped curedarticle with a thickness of about 2 mm.

The hardness and oil resistance (weight increase/IRM 903 oil, 150° C.×70hours) of the cured article were measured. The results are shown inTable 1.

Further, the mechanical properties of the cured article after aging weremeasured. The results are shown in Table 2.

Further, the compression set (25% compression/150° C.×70 hours) of thecured article after aging was measured. The result is shown in Table 3.

Example 2

0.24 Part of 2,2-diethoxyacetophenone and 1.2 parts of Irganox 1010(manufactured by Chiba Specialty Chemicals Co., Ltd.) were added to 100parts of polymer [1] obtained in Production Example 1 and 20 parts ofpolymer [2] obtained in Production Example 2 and the mixture wasadequately mixed to obtain a curable composition. The viscosity at roomtemperature (23° C.) of the composition was 300 Pa·s.

Then, the curable composition obtained was passed 3 times under a metalhalide lamp (80 W/cm, an irradiation distance of 15 cm and a belt speedof 1.0 m/min) for light irradiation to obtain a sheet shaped curedarticle with a thickness of about 2 mm.

The hardness and oil resistance (weight increase/IRM 903 oil, 150° C.×70hours) of the cured article were measured. The results are shown inTable 1.

Further, the mechanical properties of the cured article after aging weremeasured. The results are shown in Table 2.

Further, the compression set (25% compression/150° C.×70 hours) of thecured article after aging was measured. The result are shown in Table 3.

Example 3

0.30 Part of 2,2-diethoxyacetophenone and 1.5 parts of Irganox 1010(manufactured by Chiba Specialty Chemicals Co., Ltd.) were added to 100parts of polymer [1] obtained in Production Example 1 and 50 parts ofpolymer [2] obtained in Production Example 2 and the mixture wasadequately mixed to obtain a curable composition. The viscosity at roomtemperature (23° C.) of the composition was 170 Pa·s.

Then, the curable composition obtained was passed 3 times under a metalhalide lamp (80 W/cm, an irradiation distance of 15 cm and a belt speedof 1.0 m/min) for light irradiation to obtain a sheet shaped curedarticle with a thickness of about 2 mm.

The hardness and oil resistance (weight increase/IRM 903 oil, 150° C.×70hours) of the cured article were measured. The results are shown inTable 1.

Further, the mechanical properties of the cured article after aging weremeasured. The results are shown in Table 2.

Further, the compression set (25% compression/150° C.×70 hours) of thecured article after aging was measured. The result is shown in Table 3.

Example 4

0.40 Part of 2,2-diethoxyacetophenone and 2.0 parts of Irganox 1010(manufactured by Chiba Specialty Chemicals Co., Ltd.) were added to 100parts of polymer [1] obtained in Production Example 1 and 100 parts ofpolymer [2] obtained in Production Example 2 and the mixture wasadequately mixed to obtain a curable composition. The viscosity at roomtemperature (23° C.) of the composition was 120 Pa·s.

Then, the curable composition obtained was passed 3 times under a metalhalide lamp (80 W/cm, an irradiation distance of 15 cm and a belt speedof 1.0 m/min) for light irradiation to obtain a sheet shaped curedarticle with a thickness of about 2 mm.

The hardness and oil resistance (weight increase/IRM 903 oil, 150° C.×70hours) of the cured article were measured. The results are shown inTable 1.

Further, the mechanical physicality of the cured article after agingwere measured. The results are shown in Table 2.

Further, the compression set (25% compression/150° C.×70 hours) of thecured article after aging was measured. The result is shown in Table 3.

Example 5

0.24 Part of 2,2-diethoxyacetophenone and 1.2 parts of Irganox 1010(manufactured by Chiba Specialty Chemicals Co., Ltd.) were added to 100parts of polymer [1] obtained in Production Example 1, 10 parts ofpolymer [2] obtained in Production Example 2 and 10 parts of isobornylacrylate and the mixture was adequately mixed to obtain a curablecomposition. The viscosity at room temperature (23° C.) of thecomposition was 100 Pa·s.

Then, the curing composition obtained was passed 3 times under a metalhalide lamp (80 W/cm, an irradiation distance of 15 cm and a belt speedof 1.0 m/min) for light irradiation to obtain a sheet shaped curedarticle with a thickness of about 2 mm.

The hardness and oil resistance (weight increase/IRM 903 oil, 150° C.×70hours) of the cured article were measured. The results are shown inTable 1.

Further, the mechanical properties of the cured article after aging weremeasured. The results are shown in Table 2.

Further, the compression set (25% compression/150° C.×70 hours) of thecured article after aging was measured. The result is shown in Table 3.

Example 6

0.24 Part of 2,2-diethoxyacetophenone and 1.2 parts of Irganox 1010(manufactured by Chiba Specialty Chemicals Co., Ltd.) were added to 100parts of polymer [1] obtained in Production Example 1, 10 parts ofpolymer [2] obtained in Production Example 2, and 10 parts of a mixtureof acrylic monomers (a mixture of n-butyl acrylate/ethylacrylate/2-methoxyethyl acrylate=25/46/29 by mole) and the mixture wasadequately mixed to obtain a curable composition. The viscosity at roomtemperature (23° C.) of the composition was 40 Pa·s.

Then, the curable composition obtained was passed 3 times under a metalhalide lamp (80 W/cm, an irradiation distance of 15 cm and a belt speedof 1.0 m/min) for light irradiation to obtain a sheet shaped curedarticle with a thickness of about 2 mm.

The hardness and oil resistance (weight increase/IRM 903 oil, 150° C.×70hours) of the cured article were measured. The results are shown inTable 1.

Further, the mechanical properties of the cured article after aging weremeasured. The results are shown in Table 2.

Further, the compression set (25% compression/150° C.×70 hours) of thecured article after aging was measured. The result is shown in Table 3.

Comparative Example 1

0.20 Part of 2,2-diethoxyacetophenone and 1.0 part of Irganox 1010(manufactured by Chiba Specialty Chemicals Co., Ltd.) were added to 100parts of polymer [1] obtained in Production Example 1 and the mixturewas adequately mixed to obtain a curable composition. The viscosity atroom temperature (23° C.) of the composition was 510 Pa·s andworkability such as mixing and pouring was poor.

Then, the curable composition obtained was passed 3 times under a metalhalide lamp (80 W/cm, an irradiation distance of 15 cm and a belt speedof 1.0 m/min) for light irradiation to obtain a sheet shaped curedarticle with a thickness of about 2 mm.

The hardness and oil resistance (weight increase/IRM 903 oil, 150° C.×70hours) of the cured article were measured. The results are shown inTable 1.

Further, the mechanical properties of the cured article after aging weremeasured. The results are shown in Table 2.

Further, the compression set (25% compression/150° C.×70 hours) of thecured article after aging was measured. The result is shown in Table 3.

Comparative Example 2

100 g of polyoxypropylene glycol with a molecular weight of about 10,000whose ends were alkenylated, 6.9 g of linear chain siloxane containing 5hydrosilyl groups on the average and 5 α-methylstyrene groups on theaverage in a molecule, 0.64 ml of1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zerovalent platinumwere mixed at room temperature (23° C.) and the mixture was cured at150° C. for 10 minutes.

The hardness and oil resistance (weight increase/IRM 903 oil, 150° C.×70hours) of the cured article were measured. The results are shown inTable 1.

Further, the mechanical properties of the cured article after aging weremeasured. The results are shown in Table 2.

TABLE 1 Oil resistance Example Hardness (DuroA) (mass increase: %) 1 2015 2 18 14 3 13 15 4 7 13 5 18 23 6 17 16 Com. Ex. 1 22 15 Com Ex. 2 24362

TABLE 2 Example M50 (Mpa) Tb (MPa) Eb (%) 1 0.36 0.45 61 2 0.34 0.43 663 0.25 0.40 80 4 0.16 0.36 100 5 0.32 0.68 108 6 0.26 0.38 77 Com. Ex. 10.41 0.48 59 Com. Ex. 2 0.37 0.57 100

TABLE 3 Example Compression set (%) 1 3 2 4 3 3 4 2 5 3 6 5 Com. Ex. 1 4

1. An active energy curing type composition for an in-place shapinggasket, comprising the under-mentioned components (A) and (B) asessential components, wherein the viscosity of the composition is 400Pa·s or less at 23° C. and the compression set (obtained by a procedurewherein strain after compressed by 25% at 150° C. for 70 hours ismeasured and the strain which is not restored after the release ofcompression is expressed in terms of percentage, provided that thequantity of compression applied is 100%) of a cured article which isprescribed in JIS K 6262 is 30% or less (A) a vinyl polymer having twoor more groups represented by general formula (1):—OC(O)C(R^(a))═CH₂  (1)  wherein R^(a) represents a hydrogen atom or anorganic group having 1 to 20 carbon atoms, per molecule at the molecularends (B) a vinyl polymer having one group represented by general formula(1) per molecule at the molecular end.
 2. The composition for anin-place shaping gasket of claim 1, wherein the vinyl monomerconstituting the main chain of component (A) or (B) comprises a(meth)acrylic monomer as a main component.
 3. The composition for anin-place shaping gasket of claim 1, wherein the vinyl monomerconstituting the main chain of component (A) or (B) comprises an acrylicacid ester monomer as a main component.
 4. The composition for anin-place shaping gasket of claim 1, wherein the vinyl monomerconstituting the main chain of component (A) or (B) contains at least 2monomers selected from butyl acrylate, ethyl acrylate and 2-methoxyethylacrylate.
 5. The composition for an in-place shaping gasket of claim 1,wherein the viscosity of the vinyl polymer of component (B) is 100 Pa·sor less at 23° C.
 6. The composition for an in-place shaping gasket ofclaim 1, wherein R^(a) is a hydrogen atom or a hydrocarbon group having1 to 20 carbon atoms.
 7. The composition for an in-place shaping gasketof claim 6, wherein R^(a) is a hydrogen atom or a methyl group.
 8. Thecomposition for an in-place shaping gasket of claim 1, which is used forsealing a site at which oil resistance is required.
 9. The compositionfor an in-place shaping gasket of claim 1, which is used for sealing asite at which oil resistance and heat resistance are required.
 10. Thecomposition for an in-place shaping gasket of claim 1, which is used inthe periphery of the engine of an automobile.
 11. The composition for anin-place shaping gasket of claim 1, which is used for sealing the oilpan joint face of an automobile.
 12. The composition for an in-placeshaping gasket of claim 1, wherein the oil resistance of the curedarticle of the composition for an in-place shaping gasket exceeds theoil resistance of the cured article of a composition comprising apolymer in which the repeating unit of vinyl polymer main chains ofcomponents (A) and (B) is changed to butyl acrylate alone, with respectto at least one of items of the immersion test of JIS K 6258 forlubricating oil Class 3 No. 5 for road vehicle prescribed in JIS K 2215.13. The composition for an in-place shaping gasket of claim 1, whereinthe oil resistance of the cured article of the composition for anin-place shaping gasket is such that a mass change ratio after to beforeimmersion is 50% or less, in the immersion test of JIS K 6258 forlubricating oil Class 3 No. 5 for road vehicle prescribed in JIS K 2215.14. The composition for an in-place shaping gasket of claim 12, whereinmass change ratio after to before immersion is smaller than that of thecured article of a composition comprising a polymer in which therepeating unit of vinyl polymer main chains of components (A) and (B) ischanged to butyl acrylate alone, in the immersion test of JIS K 6258 forlubricating oil Class 3 No. 5 for road vehicle prescribed in JIS K 2215.15. The composition for an in-place shaping gasket of claim 12, whereinvolume change ratio after to before immersion is smaller than that ofthe cured article of a composition comprising a polymer in which therepeating unit of vinyl polymer main chains of components (A) and (B) ischanged to butyl acrylate alone, in the immersion test of JIS K 6258 forlubricating oil Class 3 No. 5 for road vehicle prescribed in JIS K 2215.16. The composition for an in-place shaping gasket of claim 1, whereincomponent (A) or (B) is produced by reacting a compound indicated bygeneral formula (2):M⁺⁻OC(O)C(R^(a))═CH₂  (2) wherein R^(a) represents a hydrogen atom or anorganic group having 1 to 20 carbon atoms and M⁺represents an alkalimetal ion or a quaternary ammonium ion, with a vinyl polymer havinghalogen group(s) at the end(s).
 17. The composition for an in-placeshaping gasket of claim 16, wherein the vinyl polymer having halogengroup(s) at the end(s) has a group indicated by general formula (3):—CR¹R²X  (3) wherein R¹ and R² represent a group bonded to theethylenically unsaturated group of a vinyl monomer, and X represents achlorine atom, a bromine atom or an iodine atom.
 18. The composition foran in-place shaping gasket of claim 1, wherein component (A) or (B) isproduced by reacting a compound indicated by general formula (4):X¹C(O)C(R^(a))═CH₂  (4) wherein R^(a) represents a hydrogen atom or anorganic group having 1 to 20 carbon atoms, and X¹ represents a chlorineatom, a bromine atom or a hydroxyl group, with a vinyl polymer havinghydroxyl group(s) at the end(s).
 19. The composition for an in-placeshaping gasket of claim 1, wherein component (A) or (B) is produced by:(1) reacting a diisocyanate compound with a vinyl polymer havinghydroxyl group(s) at the end(s), and (2) reacting a compound indicatedby general formula (5):HO—R′—OC(O)C(R^(a))═CH₂  (5)  wherein R^(a) represents a hydrogen atomor an organic group having 1 to 20 carbon atoms and R′ represents adivalent organic group having 2 to 20 carbon atoms, with the residualisocyanate group.
 20. The composition for an in-place shaping gasket ofclaim 1, wherein the main chain of component (A) or (B) is produced by aliving radical polymerization of a vinyl monomer.
 21. The compositionfor an in-place shaping gasket of claim 20, wherein the living radicalpolymerization is atom transfer radical polymerization.
 22. Thecomposition for an in-place shaping gasket of claim 21, wherein atransition metal complex being the catalyst of the atom transfer radicalpolymerization is selected from complexes of copper, nickel, rutheniumand iron.
 23. The composition for an in-place shaping gasket of claim22, wherein the transition metal complex is a complex of copper.
 24. Thecomposition for an in-place shaping gasket of claim 1, wherein the mainchain of component (A) or (B) is produced by the polymerization of avinyl monomer using a chain transfer agent.
 25. The composition for anin-place shaping gasket of claim 1, wherein component (A) has a numberaverage molecular weight of 3,000 or more.
 26. The composition for anin-place shaping gasket of claim 1, wherein the vinyl polymer ofcomponent (A) or (B) has a ratio of weight average molecular weight tonumber average molecular weight of less than 1.8 determined by gelpermeation chromatography.
 27. The composition for an in-place shapinggasket of claim 1, which further contains a photopolymerizationinitiator (C) in addition to components (A) and (B).
 28. The compositionfor an in-place shaping gasket of claim 1, which further contains amonomer and/or an oligomer having a radical polymerizable group.
 29. Thecomposition for an in-place shaping gasket of claim 1, which furthercontains a monomer and/or an oligomer having an anionic polymerizablegroup.
 30. The composition for an in-place shaping gasket of claim 28,which contains a monomer and/or an oligomer having a (meth)acryloylgroup.
 31. The composition for an in-place shaping gasket of claim 30,which contains a monomer and/or an oligomer having a (meth)acryloylgroup and having a number average molecular weight of 5,000 or less. 32.The composition for an in-place shaping gasket of claim 27, wherein thephotopolymerization initiator of component (C) is a radicalphotoinitiator.
 33. The composition for an in-place shaping gasket ofclaim 27, wherein the photopolymerization initiator of component (C) isan anionic photoinitiator.
 34. An in-place shaped gasket comprising theactive energy curing type composition for an in-place shaping gasket ofclaim
 1. 35. An in-place shaped gasket obtainable by irradiating theactive energy curing type composition for an in-place shaping gasket ofclaim 1 with active energy radiation.
 36. The in-place shaped gasket ofclaim 34, wherein the compression set (obtained by a procedure whereinstrain after compressed by 25% at 150° C. for 70 hours is measured andthe strain which is not restored after the release of compression isexpressed in terms of percentage, provided that the quantity ofcompression applied is 100%) prescribed in JIS K 6262 is 20% or less.37. The in-place shaped gasket of claim 34, wherein the compression set(obtained by a procedure wherein strain after compressed by 25% at 150°C. for 70 hours is measured and the strain which is not restored afterthe release of compression is expressed in terms of percentage, providedthat the quantity of compression applied is 100%) prescribed in JIS K6262 is 10% or less.
 38. An active energy curing type composition for anin-place shaping gasket, which is obtainable by mixing theunder-mentioned components (A) and (B), wherein the viscosity of thecomposition is 400 Pa·s or less at 23° C. and the compression set(obtained by a procedure wherein strain after compressed by 25% at 150°C. for 70 hours is measured and the strain which is not restored afterthe release of compression is expressed in terms of percentage, providedthat the quantity of compression applied is 100%) of a cured articlewhich is prescribed in JIS K 6262 is 30% less (A) a mixture containingvinyl polymers having two or more groups represented by general formula(1):—OC(O)C(R^(a))═CH₂  (1)  wherein R^(a) represents a hydrogen atom or anorganic group having 1 to 20 carbon atoms, per molecule at the molecularends, in which the number of groups represented by general formula (1)in the vinyl polymers is 1.1 or more on the average (B) a mixturecontaining vinyl polymers having one group represented by generalformula (1) per molecule at the molecular end, in which the number ofgroups represented by general formula (1) in the vinyl polymers is 1.0or less on the average.